Particulate superabsorbent polymer composition having improved stability and fast absorption

ABSTRACT

The present invention relates to a fast particulate superabsorbent polymer composition comprising a polymer comprising a neutralized aluminum salt solution applied to the surface of a particulate superabsorbent polymer; wherein an aqueous solution of the neutralized aluminum salt has a pH value from about 5.5 to about 8; and subsequent to subjecting the particulate superabsorbent polymer composition to the Processing Test, the particulate superabsorbent polymer composition has a permeability stability index of from about 0.60 to about 0.99, and a compressibility from 1.30 mm 2 /N to about 4 mm 2 /N as measured by the Compression Test, and wherein the particulate superabsorbent polymer composition may have a Vortex time of from 25 to 60 seconds and absorbency under load at 0.9 psi of from 15 to 21 g/g.

This application claims priority pursuant to 35 U.S.C. §119(e) to U.S.patent application Ser. No. 13/860,019, filed on Apr. 10, 2013, and toU.S. Continuation-In-Part patent application Ser. No. 14/157,769, filedon Jan. 17, 2014, which are hereby incorporated by reference in theirentireties.

FIELD OF THE INVENTION

The present invention relates to particulate superabsorbent polymercompositions which absorb water, aqueous liquids, and blood, and amethod to make the particulate superabsorbent polymer compositions. Inparticular, the present invention relates to particulate superabsorbentpolymer compositions having high permeability and improved stability ofthe particulate superabsorbent polymer compositions after processing.This invention is also directed to improving the stability of theproperties of the particulate superabsorbent polymer compositionsincluding permeability.

BACKGROUND OF THE INVENTION

A superabsorbent polymer, in general refers to a water-swellable,water-insoluble polymer, or material, capable of absorbing at leastabout 10 times its weight, and up to about 30 times or more its weightin an aqueous solution containing 0.9 weight percent sodium chloridesolution in water. Examples of superabsorbent polymer may include acrosslinked partially neutralized acrylate polymer, and the formation ofsuperabsorbent hydrogel from the polymerization, and formation ofparticulate superabsorbent polymer compositions capable of retaining theaqueous liquids under a certain pressure in accordance with the generaldefinition of superabsorbent polymer.

The superabsorbent polymer hydrogel can be formed into particles,generally referred to as particulate superabsorbent polymer, wherein theparticulate superabsorbent polymer may be surface-treated with surfacecrosslinking, and other surface treatment and post treated after surfacecrosslinking to form particulate superabsorbent polymer compositions.The acronym SAP may be used in place of superabsorbent polymer,superabsorbent polymer composition, particulate superabsorbent polymercompositions, or variations thereof. Commercial particulatesuperabsorbent polymer compositions are widely used in a variety ofpersonal care products, such as infant diapers, child training pants,adult incontinence products, feminine care products, and the like. Ingeneral, these particulate superabsorbent polymer compositions have acentrifuge retention capacity (CRC) of at least 25 grams of 0.9 weightpercent sodium chloride aqueous solution per gram of the polymer.Particulate superabsorbent polymer compositions are also designed toquickly uptake bodily fluids, which requires a reasonable absorptionspeed, and are designed to quickly distribute fluids in highconcentrations, which requires high permeability, which can be measuredas high gel bed permeability (GBP). Commercial particulatesuperabsorbent polymer compositions undergo significant processingduring manufacturing and converting processes, resulting in lack ofstability of the original gel bed permeability. This lack of stabilityor reduction of the value of various properties, including gel bedpermeability may be one of the causes of premature leakage and skinwetness problems for absorbent articles.

There is thus a need or desire for particulate superabsorbent polymercompositions that can withstand absorbent product manufacturing andconverting processes without resulting in a significant reduction inproperties. There is a further need or desire for a method of increasingthe permeability stability of a particulate superabsorbent polymercomposition.

SUMMARY OF THE INVENTION

The present invention is directed to a particulate superabsorbentpolymer composition having improved stability comprising a particulatesuperabsorbent polymer comprising from about 0.05 to about 2.0 wt. %based on the total amount of the polymerizable unsaturated acid groupcontaining monomer solution of a foaming agent, and from about 0.001 toabout 1.0 wt. % based on the total amount of the polymerizableunsaturated acid group containing monomer solution of a mixture of alipophile surfactant and a polyethoxylated hydrophilic surfactant, andfrom 0.01 wt % to about 5 wt % based on the particulate superabsorbentpolymer composition weight of a neutralized aluminum salt applied to thesurface of the particulate superabsorbent polymer, in the form of anaqueous neutralized aluminum salt solution having a pH value from about5.5 to about 8; wherein the particulate superabsorbent polymercomposition has a centrifuge retention capacity of from about 25 gramsto about 40 grams of 0.9 weight percent sodium chloride aqueous per gramof the particulate superabsorbent polymer composition; and an absorbencyunder load at 0.9 psi prior to subjecting the particulate superabsorbentpolymer composition to the Processing Test of from 15 g/g to 21 g/g; andhas an original Free Swell Gel Bed Permeability (FSGBP) of from about30×10-8 cm2 to about 200×10⁻⁸ cm² prior to subjecting the particulatesuperabsorbent polymer composition to the Processing Test; has a Vortextime of from 25 to 60 seconds as measured by the Vortex Test, and has apermeability stability index of from about 0.60 to about 0.99 whensubjecting the particulate superabsorbent polymer composition to aProcessing Test; and a compressibility of from 1.30 mm²/N to about 4mm²/N as measured by the Compression Test. In general, the propertiesare measured before the Processing Test unless otherwise specified.

In addition, the present invention is directed to a particulatesuperabsorbent polymer composition comprising a particulatesuperabsorbent polymer comprising an internal crosslinker agentcomprising a silane compound comprising at least one vinyl group orallyl group and at least one Si—O bond wherein the vinyl group or allylgroup is directly attached to a silicon atom, and from 0.01 wt % toabout 5 wt % based on the particulate superabsorbent polymer compositionweight of a neutralized aluminum salt applied to the surface of theparticulate superabsorbent polymer, in the form of an aqueousneutralized aluminum salt solution having a pH value from about 5.5 toabout 8; wherein the particulate superabsorbent polymer composition hasa Centrifuge Retention Capacity (CRC) of from about 25 grams to about 40grams of 0.9 weight percent sodium chloride aqueous per gram of theparticulate superabsorbent polymer composition, wherein the CRC ismeasured either before or after subjecting the superabsorbent polymercomposition to a Processing Test, and an absorbency under load at 0.9psi prior to subjecting the particulate superabsorbent polymercomposition to the Processing Test of from 15 g/g to 21 g/g; and anoriginal Free Swell Gel Bed Permeability (FSGBP) of from about 30×10⁻⁸cm² to about 200×10⁻⁸ cm² prior to subjecting the particulatesuperabsorbent polymer composition to the Processing Test; and has apermeability stability index of from about 0.60 to about 0.99 whensubjecting the particulate superabsorbent polymer composition to aProcessing Test; and a compressibility of from about 1.30 mm²/N to about4 mm²/N, and a Centrifuge Retention Capacity (CRC) Increase of 2 g/g ormore based on

CRC Increase=CRC(bt,5 hr)−CRC(rt,0.5 hr)

wherein CRC Increase measures the increase in the CRC that occurs and iscalculated as the difference between the second CRC Test and first CRCTest, and bt refers to body temperature and rt refers to roomtemperature.

In addition, the present invention is directed to a particulatesuperabsorbent polymer composition having improved stability comprising:

a) from about 55 wt % to about 85 wt % of polymerizable unsaturated acidgroup containing monomers selected from acrylic acid, methacrylic acid,or 2-acrylamido-2-methylpropanesulfonic acid, or mixtures thereof;

b) from about 14 wt % to about 45 wt % of an alkali base selected fromsodium hydroxide or potassium hydroxide to neutralize the polymerizableunsaturated acid group containing monomers of a) to from about 50 toabout 80 mol %;

c) from about 0.001 wt % to about 5.0 wt % based on the weight of a) ofan internal crosslinking agent,

d) from about 0.05 to about 2.0 wt. % based on the total amount of thepolymerizable unsaturated acid group containing monomer solution of afoaming agent, and from about 0.001 to about 1.0 wt. % based on thetotal amount of the polymerizable unsaturated acid group containingmonomer solution of a mixture of a lipophile surfactant and apolyethoxylated hydrophilic surfactant, wherein the components a), b),c) and d) are polymerized into a hydrogel which is granulated intoparticulate superabsorbent polymer having a surface;

e) from about 0.001 wt % to about 5.0 wt % based on the particulatesuperabsorbent composition weight of surface crosslinking agent appliedto the surface of the particulate superabsorbent polymer;

f) from 0.001 wt to about 5.0 wt % based on the particulatesuperabsorbent composition weight of a neutralized aluminum salt appliedto the surface of the particulate superabsorbent polymer, in the form ofan aqueous neutralized aluminum salt solution having a pH value fromabout 5.5 to about 8;

wherein the particulate superabsorbent polymer composition has acentrifuge retention capacity of from about 25 grams to about 40 gramsof 0.9 weight percent sodium chloride aqueous per gram of theparticulate superabsorbent polymer composition; and an absorbency underload at 0.9 psi prior to subjecting the particulate superabsorbentpolymer composition to the Processing Test of from 15 g/g to 21 g/g; andan original Free Swell Gel Bed Permeability (FSGBP) of about 30×10⁻⁸ cm²to about 200×10⁻⁸ cm² prior to subjecting the particulate superabsorbentpolymer composition to the Processing Test; and subsequent to subjectingthe particulate superabsorbent polymer composition to the ProcessingTest the particulate superabsorbent polymer composition has apermeability stability index of from about 0.60 to about 0.99, and aVortex time of from 25 to 60 seconds as measured by the Vortex Test, anda compressibility of from 1.30 mm²/N to about 4 mm²/N as measured by theCompression Test.

With the foregoing in mind, it is a feature and advantage of theinvention to provide particulate superabsorbent polymer compositionhaving improved permeability stability, and methods of increasingimproved stability of particulate superabsorbent polymer composition.Numerous other features and advantages of the present invention willappear from the following description.

BRIEF DESCRIPTION OF THE DRA WINGS

FIG. 1 is a side view of the test apparatus employed for the Free SwellGel Bed Permeability Test;

FIG. 2 is a cross-sectional side view of a cylinder/cup assemblyemployed in the Free Swell Gel Bed Permeability Test apparatus shown inFIG. 1;

FIG. 3 is a top view of a plunger employed in the Free Swell Gel BedPermeability Test apparatus shown in FI G 1; and

FIG. 4 is a side view of the test apparatus employed for the AbsorbencyUnder Load Test.

DEFINITIONS

Within the context of this specification, each term or phrase below willinclude the following meaning or meanings

It should be noted that, when employed in the present disclosure, theterms “comprises,” “comprising,” and other derivatives from the rootterm “comprise” are intended to be open-ended terms that specify thepresence of any stated features, elements, integers, steps, orcomponents, and are not intended to preclude the presence or addition ofone or more other features, elements, integers, steps, components, orgroups thereof.

As used herein, the term “about” modifying the quantity of an ingredientin the compositions of the invention or employed in the methods of theinvention refers to variation in the numerical quantity that can occur,for example, through typical measuring and liquid handling proceduresused for making concentrates or use solutions in the real world; throughinadvertent error in these procedures; through differences in themanufacture, source, or purity of the ingredients employed to make thecompositions or carry out the methods; and the like. The term about alsoencompasses amounts that differ due to different equilibrium conditionsfor a composition resulting from a particular initial mixture. Whetheror not modified by the term “about,” the claims include equivalents tothe quantities.

The term “Centrifuge Retention Capacity (CRC)” as used herein refers tothe ability of the particulate superabsorbent polymer to retain liquidtherein after being saturated and subjected to centrifugation undercontrolled conditions and is stated as grams of liquid retained per gramweight of the sample (g/g) as measured by the Centrifuge RetentionCapacity Test set forth herein.

The term “Centrifuge Retention Capacity Increase (CRCI)” or “CRCIncrease” or “Capacity Increase” is defined as the increase in the CRCthat occurs and is calculated as the difference between a second CRC anda first CRC. As used herein, the term “first CRC” or “initial CRC”generally refers to CRC(rt, 0.5 hr) wherein rt refers to roomtemperature of about 23° C., although another CRC value may be used. The“second CRC” may be tested at body temperature or higher, preferablyfrom about 37° C., for at least about 1 hour, preferably from about 2hours to 24 hours. The CRC Increase is measured according to the CRCIncrease Test Method described herein below.

The term “compressibility” as used herein refers to a measure of therelative volume change of the particulate superabsorbent polymercomposition as a response to a pressure change as set forth in aCompressibility Test disclosed herein.

The terms “crosslinked”, “crosslink”, “crosslinker”, or “crosslinking”as used herein refers to any means for effectively rendering normallywater-soluble materials substantially water-insoluble but swellable.Such a crosslinking means can include, for example, physicalentanglement, crystalline domains, covalent bonds, ionic complexes andassociations, hydrophilic associations such as hydrogen bonding,hydrophobic associations, or Van der Waals forces.

The term “internal crosslinker” or “monomer crosslinker” as used hereinrefers to use of a crosslinker in the monomer solution to form thepolymer.

The term “dry particulate superabsorbent polymer composition” as usedherein generally refers to the superabsorbent polymer composition havingless than about 20% moisture.

The term “gel permeability” is a property of the mass of particles as awhole and is related to particle size distribution, particle shape, andthe connectedness of the open pores between the particles, shearmodulus, and surface modification of the swollen gel. In practicalterms, the gel permeability of the superabsorbent polymer composition isa measure of how rapidly liquid flows through the mass of swollenparticles. Low gel permeability indicates that liquid cannot flowreadily through the superabsorbent polymer composition, which isgenerally referred to as gel blocking, and that any forced flow ofliquid (such as a second application of urine during use of the diaper)must take an alternate path (e.g., diaper leakage).

The acronym “HLB” means the hydrophilic-lipophilic balance of asurfactant and is a measure of the degree to which it is hydrophilic orlipophilic, as determined by calculating values for the differentregions of the molecule. The HLB value can be used to predict thesurfactant properties of a molecule wherein a HLB value<10 is lipidsoluble (water insoluble) and a HLB value>10 is water soluble (lipidinsoluble).

The terms “particle,” “particulate,” and the like, when used with theterm “superabsorbent polymer,” refer to the form of discrete units. Theunits can comprise flakes, fibers, agglomerates, granules, powders,spheres, pulverized materials, or the like, as well as combinationsthereof. The particles can have any desired shape: for example, cubic,rod like polyhedral, spherical or semi-spherical, rounded orsemi-rounded, angular, irregular, et cetera.

The terms “particulate superabsorbent polymer” and “particulatesuperabsorbent polymer composition” refer to the form of superabsorbentpolymer and superabsorbent polymer compositions in discrete form,wherein the “particulate superabsorbent polymer” and “particulatesuperabsorbent polymer compositions” may have a particle size of lessthan 1000 μm, or from about 150 μm to about 850 μm.

The term “permeability”, when used herein shall mean a measure of theeffective connectedness of a porous structure, in this case, crosslinkedpolymers, and may be specified in terms of the void fraction, and extentof connectedness of the particulate superabsorbent polymer composition.

The term “permeability stability index” when used herein shall mean theability of the particulate superabsorbent polymer to maintain theoriginal permeability after being subjected to a processing test undercontrolled conditions. It refers to the ratio of the permeability of theprocessed sample to the permeability of the original sample as set forthin a Processing Test disclosed herein.

The term “polymer” includes, but is not limited to, homopolymers,copolymers, for example, block, graft, random, and alternatingcopolymers, terpolymers, etc., and blends and modifications thereof.Furthermore, unless otherwise specifically limited, the term “polymer”shall include all possible configurational isomers of the material.These configurations include, but are not limited to isotactic,syndiotactic, and atactic symmetries.

The term “polyolefin” as used herein generally includes, but is notlimited to, materials such as polyethylene, polypropylene,polyisobutylene, polystyrene, ethylene vinyl acetate copolymer, and thelike, the homopolymers, copolymers, terpolymers, etc., thereof, andblends and modifications thereof. The term “polyolefin” shall includeall possible structures thereof, which include, but are not limited to,isotatic, synodiotactic, and random symmetries. Copolymers includeatactic and block copolymers. The term “polysiloxane” as used hereinrefers to polymerized siloxanes consisting of an inorganicsilicon-oxygen backbone ( . . . —Si—O—Si—O—Si—O— . . . ) with organicside groups attached to the silicon atoms, which are four-coordinate.Furthermore, unless otherwise specifically limited, the term“polysiloxane” should include polymers comprising two of more siloxanerepeating units.

The term “superabsorbent polymer” as used herein refers towater-swellable, water-insoluble organic or inorganic materialsincluding superabsorbent polymers and superabsorbent polymercompositions capable, under the most favorable conditions, of absorbingat least about 10 times their weight, or at least about 15 times theirweight, or at least about 25 times their weight in an aqueous solutioncontaining 0.9 weight percent sodium chloride.

The term “superabsorbent polymer composition” as used herein refers to asuperabsorbent polymer comprising a surface additive in accordance withthe present invention.

The term “surface crosslinking” as used herein refers to the level offunctional crosslinks in the vicinity of the surface of thesuperabsorbent polymer particle, which is generally higher than thelevel of functional crosslinks in the interior of the superabsorbentpolymer particle. As used herein, “surface” describes the outer-facingboundaries of the particle.

The term “thermoplastic” as used herein describes a material thatsoftens when exposed to heat and which substantially returns to anon-softened condition when cooled to room temperature.

The term “vortex time” measures the amount of time in seconds requiredfor 2 grams of a SAP to close a vortex created by stirring 50milliliters of saline solution at 600 revolutions per minute on amagnetic stir plate. The time it takes for the vortex to close is anindication of the free swell absorbing rate of the SAP.

The term “% by weight” or “% wt” as used herein and referring tocomponents of the dry particulate superabsorbent polymer composition, isto be interpreted as based on the weight of the dry superabsorbentpolymer composition, unless otherwise specified herein.

The term “moisture content” when used herein shall mean the quantity ofwater contained in the particulate superabsorbent polymer composition asmeasured by the Moisture Content Test.

These terms may be defined with additional language in the remainingportions of the specification.

DETAILED DESCRIPTION OF THE INVENTION

While typical aspects of embodiment and/or embodiments have been setforth for the purpose of illustration, this Detailed Description and theaccompanying drawings should not be deemed to be a limitation on thescope of the invention. Accordingly, various modifications, adaptations,and alternatives may occur to one skilled in the art without departingfrom the spirit and scope of the present invention. By way of ahypothetical illustrative example, a disclosure in this specification ofa range of from 1 to 5 shall be considered to support claims to any ofthe following ranges: 1-5; 1-4; 1-3; 1-2; 2-5; 2-4; 2-3; 3-5; 3-4; and4-5.

In accordance with the invention, a particulate superabsorbent polymercomposition having improved stability can be achieved using the methodsdescribed herein. These particulate superabsorbent polymer compositionshaving improved stability have improved resistance to processing of theparticulate superabsorbent polymer composition, and reduced functionalloss compared to current commercially available particulatesuperabsorbent polymer composition.

In another embodiment, the present invention is directed to aparticulate superabsorbent polymer composition having improved stabilitycomprising a particulate superabsorbent polymer comprising from about0.05 to about 2.0 wt. % based on the total amount of the polymerizableunsaturated acid group containing monomer solution of a foaming agent,and from about 0.001 to about 1.0 wt. % based on the total amount of thepolymerizable unsaturated acid group containing monomer solution of amixture of a lipophile surfactant and a polyethoxylated hydrophilicsurfactant, and from 0.01 wt % to about 5 wt % based on the particulatesuperabsorbent polymer composition weight of a neutralized aluminum saltapplied to the surface of the particulate superabsorbent

polymer, in the form of an aqueous neutralized aluminum salt solutionhaving a pH value from about 5.5 to about 8; wherein the particulatesuperabsorbent polymer composition has a centrifuge retention capacityof from about 25 grams to about 40 grams of 0.9 weight percent sodiumchloride aqueous per gram of the particulate superabsorbent polymercomposition; and an absorbency under load at 0.9 psi prior to subjectingthe particulate superabsorbent polymer composition to the ProcessingTest of from 15 g/g to 21 g/g; and an original Free Swell Gel BedPermeability (FSGBP) of about 30×10−8 cm2 to about 200×10⁻⁸ cm² prior tosubjecting the treated particulate superabsorbent polymer composition toa Processing Test; wherein the particulate superabsorbent polymercomposition has a Vortex time of from 25 to 60 seconds as measured bythe Vortex Test; and has a permeability stability index of from about0.60 to about 0.99 when subjecting the particulate superabsorbentpolymer composition to a Processing Test; and a compressibility of from1.30 mm²/N to about 4 mm²/N as measured by the Compression Test.

In addition, the present invention is directed to a particulatesuperabsorbent polymer composition having improved stability comprising:

a) from about 55 wt % to about 85 wt % of polymerizable unsaturated acidgroup containing monomers selected from acrylic acid, methacrylic acid,or 2-acrylamido-2-methylpropanesulfonic acid, or mixtures thereof;

b) from about 14 wt % to about 45 wt % of an alkali base selected fromsodium hydroxide or potassium hydroxide to neutralize the polymerizableunsaturated acid group containing monomers of a) to from about 50 toabout 80 mol %;

c) from about 0.001 wt % to about 5.0 wt % based on the weight of a) ofan internal crosslinking agent;

d) from about 0.05 to about 2.0 wt. % based on the total amount of thepolymerizable unsaturated acid group containing monomer solution of afoaming agent, and from about 0.001 to about 1.0 wt. % based on thetotal amount of the polymerizable unsaturated acid group containingmonomer solution of a mixture of a lipophile surfactant and apolyethoxylated hydrophilic surfactant, wherein the components a), b),c), and d) are polymerized into a hydrogel which is granulated intoparticulate superabsorbent polymer having a surface;

e) from about 0.001 wt % to about 5.0 wt % based on the particulatesuperabsorbent composition weight of surface crosslinking agent appliedto the surface of the particulate superabsorbent polymer;

f) from 0.001 wt to about 5.0 wt % based on the particulatesuperabsorbent composition weight of a neutralized aluminum salt appliedto the surface of the particulate superabsorbent polymer, in the form ofan aqueous neutralized aluminum salt solution having a pH value fromabout 5.5 to about 8;

wherein the particulate superabsorbent polymer composition has acentrifuge retention capacity of from about 25 grams to about 40 gramsof 0.9 weight percent sodium chloride aqueous per gram of theparticulate superabsorbent polymer composition; and an absorbency underload at 0.9 psi prior to subjecting the particulate superabsorbentpolymer composition to the Processing Test of from 15 g/g to 21 g/g; andan original Free Swell Gel Bed Permeability (FSGBP) of about 30×10⁻⁸ cm²to about 200×10⁻⁸ cm² prior to subjecting the treated particulatesuperabsorbent polymer composition to the Processing Test; andsubsequent to subjecting the treated particulate superabsorbent polymercomposition to the Processing Test the treated particulatesuperabsorbent polymer composition has a permeability stability index offrom about 0.60 to about 0.99 when subjecting the particulatesuperabsorbent polymer composition to a Processing Test; and has aVortex time of from 25 to 60 seconds as measured by the Vortex Test; anda compressibility of from 1.30 mm²/N to about 4 mm²/N as measured by theCompression Test.

In another embodiment, the invention is directed to a process for theproduction of a particulate superabsorbent polymer compositioncomprising the following steps:

A) preparing a process for making a particulate superabsorbent polymerhaving fast water absorption comprising the steps of

a) preparing an aqueous monomer solution of a mixture of a ofpolymerizable unsaturated acid group containing monomer and an internalcrosslinking agent monomer wherein the aqueous monomer solutioncomprises dissolved oxygen;

b) sparging the aqueous monomer solution of step a) including adding aninert gas to the aqueous monomer solution of step a) to replace thedissolved oxygen of the aqueous monomer solution;

c) polymerizing the aqueous monomer solution of step b) including thesteps of

c1) adding to the aqueous monomer solution of step a): i) an aqueoussolution comprising from about 0.05 to about 2.0 wt. % based on thetotal amount of the polymerizable unsaturated acid group containingmonomer solution of a foaming agent; and ii) an aqueous solutioncomprising from about 0.001 to about 1.0 wt. % based on the total amountof the polymerizable unsaturated acid group containing monomer solutionof a mixture of a lipophile surfactant and a polyethoxylated hydrophilicsurfactant;

c2) treating the monomer solution of step c1) to high speed shear mixingto form a treated monomer solution, wherein the components i) an aqueoussolution comprising from about 0.1 to about 1.0 wt. % of a foamingagent; and ii) an aqueous solution comprising from about 0.001 to about1.0 wt. % of a mixture of a lipophile surfactant and a polyethoxylatedhydrophilic surfactant are added to the aqueous monomer solution afterstep b) of sparging the aqueous monomer solution and before step c2) ofhigh speed shear mixing of the aqueous monomer solution;

c3) forming a hydrogel by adding a polymerization initiator to thetreated monomer solution of step c2) wherein the initiator is added tothe treated monomer solution after the foaming agent and the mixture ofsurfactants, wherein the polymer is formed to include bubbles of thefoaming agent into the polymer structure; and

d) drying and grinding the hydrogel of step c) to form particulatesuperabsorbent polymer; and

e) surface crosslinking the particulate superabsorbent polymer of stepd) with a surface crosslinking agent;

B preparing a neutralized aluminum salt in the form of an aqueoussolution having a pH value from about 5.5 to about 8; and;

C applying the aqueous neutralized aluminum salt solution on the surfaceof the particulate superabsorbent polymer; and

wherein the particulate superabsorbent polymer composition has a degreeof neutralization of from about 50% mol to about 80 mol %; and theparticulate superabsorbent polymer composition has a CentrifugeRetention Capacity of from about 25 grams to about 40 grams of 0.9weight percent sodium chloride aqueous per gram of the particulatesuperabsorbent polymer composition, wherein the CRC is measured eitherbefore or after subjecting the superabsorbent polymer composition to aProcessing Test, and an absorbency under load at 0.9 psi prior tosubjecting the particulate superabsorbent polymer composition to theProcessing Test of from 15 g/g to 21 g/g; and a Free Swell Gel BedPermeability (FSGBP) of about 30×10⁻⁸ cm² to about 200×10⁻⁸ cm² prior tosubjecting the treated particulate superabsorbent polymer composition tothe Processing Test; has a permeability stability index of from about0.60 to about 0.99 when subjecting the particulate superabsorbentpolymer composition to a Processing Test; and a compressibility from1.30 mm2 IN to about 4 mm2 IN as measured by the Compression Test; andthe wherein the surface crosslinked superabsorbent polymer has a vortexof from about 25 sec to about 60 sec.

The present invention is also directed to a particulate superabsorbentpolymer composition having improved stability comprising a particulatesuperabsorbent polymer comprising a silane compound crosslinkercomprising at least one vinyl group or allyl group and at least one Si—Obond wherein the vinyl group or allyl group is directly attached to asilicon atom, wherein the particulate superabsorbent polymer has aCentrifuge Retention Capacity (CRC) Increase of 2 g/g or more based on

CRC Increase=CRC(bt,5hr)−CRC(rt,0.5hr)

wherein CRC Increase measures the increase in the CRC that occurs and iscalculated as the difference between the second CRC Test and first CRCTest, and bt refers to body temperature and rt refers to roomtemperature, and from 0.01 wt % to about 5 wt % based on the particulatesuperabsorbent polymer composition weight of a neutralized aluminum saltapplied to the surface of the particulate superabsorbent polymer, in theform of an aqueous neutralized aluminum salt solution having a pH valuefrom about 5.5 to about 8; wherein the particulate superabsorbentpolymer composition has a centrifuge retention capacity of from about 25grams to about 40 grams of 0.9 weight percent sodium chloride aqueousper gram of the particulate superabsorbent polymer composition; and anabsorbency under load at 0.9 psi prior to subjecting the particulatesuperabsorbent polymer composition to the Processing Test of from 15 g/gto 21 g/g; and an original Free Swell Gel Bed Permeability (FSGBP) ofabout 30×10⁻⁸ cm² to about 200×10⁻⁸ cm² prior to subjecting theparticulate superabsorbent polymer composition to a Processing Test; hasa permeability stability index of from about 0.60 to about 0.99 whensubjecting the particulate superabsorbent polymer composition to aProcessing Test; and a compressibility of from about 1.30 mm2/N to about4 mm2/N as measured by the Compression Test.

A suitable superabsorbent polymer may be selected from synthetic,natural, biodegradable, and modified natural polymers. The termcrosslinked used in reference to the superabsorbent polymer refers toany means for effectively rendering normally water-soluble materialssubstantially water-insoluble but swellable. Such a crosslinking meanscan include for example, physical entanglement, crystalline domains,covalent bonds, ionic complexes and associations, hydrophilicassociations such as hydrogen bonding, hydrophobic associations or Vander Waals forces. Superabsorbent polymers include internal crosslinkingand may further include surface crosslinking

A superabsorbent polymer as set forth in embodiments of the presentinvention can be obtained by the initial polymerization of from about55% to about 99.9 wt % of the superabsorbent polymer of polymerizableunsaturated acid group containing monomer. A suitable monomer includesany of those containing carboxyl groups, such as acrylic acid ormethacrylic acid; or 2-acrylamido-2-methylpropanesulfonic acid, ormixtures thereof. It is desirable for at least about 50 wt %, and moredesirable for at least about 75 wt % of the acid groups to be carboxylgroups.

The process to make a superabsorbent polymer as set forth in embodimentsof the present invention may be obtained by the initial polymerizationof from about 55% to about 99.9 wt % of the superabsorbent polymer ofpolymerizable unsaturated acid group containing monomer. A suitablepolymerizable monomer includes any of those containing carboxyl groups,such as acrylic acid, methacrylic acid, or2-acrylamido-2-methylpropanesulfonic acid, or mixtures thereof. It isdesirable for at least about 50% by weight, and more desirable for atleast about 75 wt % of the acid groups to be carboxyl groups.

The acid groups are neutralized with an alkali metal base to the extentof at least about 25 mol %, or from about 50 mol % to about 80 mol %,that is, the acid groups are desirably present as sodium, potassium, orammonium salts. The amount of alkali base may be from about 14 wt % toabout 45 wt % of the particulate superabsorbent polymer composition. Thealkali base may include sodium hydroxide or potassium hydroxide. In someaspects, it is desirable to utilize polymers obtained by polymerizationof acrylic acid or methacrylic acid, the carboxyl groups of which areneutralized in the presence of internal cross linking agents. It isnoted that the neutralization may be achieved by either adding thealkali base to the monomer solution or adding the monomer such asacrylic acid to the alkali base.

In some aspects, the second suitable monomer that can be copolymerizedwith the ethylenically unsaturated monomer may include, but is notlimited to acrylamide, methacrylamide, hydroxyethyl acrylate,dimethylaminoalkyl (meth)-acrylate, ethoxylated (meth)-acrylates,dimethylaminopropylacrylamide, or acrylamidopropyltrimethylammoniumchloride. Such monomer may be present in a range of from 0 wt % to about40 wt % of the copolymerized monomer.

In the case when the monomer is acrylic acid, the partially neutralized,acrylate salt is turned into the polymer in the particulate waterabsorbing agent following polymerization, the converted value based onacrylic acid may be determined through converting the partiallyneutralized polyacrylate salt is assumed to be entirely the equimolarunneutralized polyacrylic acid.

The superabsorbent polymer of the invention also includes from about0.001 wt % to about 5 wt % by weight or from about 0.2 wt % to about 3wt % based on the total amount of the polymerizable unsaturated acidgroup containing monomer of at least one internal cross linking agent.The internal crosslinking agent generally has at least two ethylenicallyunsaturated double bonds or one ethylenically unsaturated double bondand one functional group which is reactive towards acid groups of thepolymerizable unsaturated acid group containing monomers or severalfunctional groups which are reactive towards acid groups can be used asthe internal crosslinking component and which is present during thepolymerization of the polymerizable unsaturated acid group containingmonomers.

Examples of internal crosslinking agents used in superabsorbent polymersinclude aliphatic unsaturated amides, such as methylenebisacryl- or-methacrylamide or ethylenebisacrylamide, and furthermore aliphaticesters of polyols or alkoxylated polyols with ethylenically unsaturatedacids, such as di(meth)acrylates or tri(meth)acrylates of butanediol orethylene glycol, polyglycols or trimethylolpropane, di- and triacrylateesters of trimethylolpropane which is preferably oxyalkylated,preferably ethoxylated, with 1 to 30 mol of alkylene oxide, acrylate andmethacrylate esters of glycerol and pentaerythritol and of glycerol andpentaerythritol oxyethylated with preferably 1 to 30 mol of ethyleneoxide and furthermore allyl compounds, such as allyl (meth)acrylate,alkoxylated allyl (meth)acrylate reacted with preferably 1 to 30 mol ofethylene oxide, triallyl cyanurate, triallyl isocyanurate, maleic aciddiallyl ester, poly-allyl esters, vinyl trimethoxysilane, vinyltriethoxysilane, polysiloxane comprising at least two vinyl groups,tetraallyloxyethane, tetraallyloxyethane, triallylamine,tetraallylethylenediamine, diols, polyols, hydroxy allyl or acrylatecompounds and allyl esters of phosphoric acid or phosphorous acid, andfurthermore monomers which are capable of crosslinking, such asN-methylol compounds of unsaturated amides, such as of methacrylamide oracrylamide, and the ethers derived there from. Ionic crosslinkers suchas aluminum metal salts may also be employed. Mixtures of thecrosslinking agents mentioned can also be employed.

The internal crosslinker agent may contain a silane compound comprisingat least one vinyl group or allyl group directly attached to a siliconatom and at least one Si—O bond. The silane compound may be selectedfrom one of the following:

wherein

R₁ represents C₂ to C₃ alkenyl,

R₂ represents H, C₁ to C₄ alkyl, C₂ to C₅ alkenyl, C₆ to C₈ aryl, C₂ toC₅ carbonyl,

R₃ represents H, C₁ to C₄ alkyl, C₆ to C₈ aryl,

R₄ and R₅ independently represent H, C₁ to C₄ alkyl, C₆ to C₈ aryl,

m represents an integer of from 1 to 3, preferably 1 to 2,

n represents an integer of from 1 to 3, preferably 2 to 3,

l represents an integer of from 0 to 2, preferably 0 to 1,

m+n+1=4,

x represents an integer larger than 1, and

y represents an integer of 0 or larger than 0.

Illustrative of silanes, having at least one vinyl group or allyl groupdirectly attached to a silicon atom and a Si—O bond, which may beutilized to provide the structure in formula (I) above include:vinylalkoxysilanes such as vinyltrimethoxysilane,methylvinyltrimethoxysilane, vinyltriethoxysilane,methylvinyltriethoxysilane, vinylmethyldimethoxysilane,vinylethyldiethoxysilane, and vinyltris(2-methoxyethoxy)silane;vinylacetoxysilanes, such as vinylmethyldiacetoxysilane,vinylethyldiacetoxysilane and vinyltriacetoxysilane; allylalkoxysilanessuch as allyltrimethoxysilane, allylmethyldimethoxysilane, andallyltriethoxysilane; divinylalkoxysilanes and divinylacetoxysilanessuch as divinyldimethoxysilane, divinyldiethoxysilane anddivinyldiacetoxysilane; diallylalkoxysilanes and diallylacetoxysilanessuch as diallyldimethoxysilane, diallyldiethoxysilane anddiallyldiacetoxysilane; as well as other similar ethylenicallyunsaturated silane monomers containing one or more hydrolyzable groups.As will be appreciated by one skilled in the art given the presentdisclosure, use of compounds such as vinyltrichlorosilane in water oralcohol can provide structures in formula (I) above in which, forexample, the group R₁ can be a vinyl group. It is also possible thatmore complex structures can be formed, for example, by reaction of vinylsilane with polyethylene glycol.

Illustrative of polysiloxanes, having at least one vinyl group or allylgroup directly attached to a silicon atom, which may be utilized toprovide the structure in formula (II) or (III) above include thepolymers and copolymers of silanes having the structure in formula (I).Preferred examples include, but not limited to, polysiloxane comprisingvinyl and methoxy groups (commercially available from Evonik DegussaCorporation, under the trade designation Dynasylan® 6490), polysiloxanecomprising vinyl and ethoxy groups (commercially available from EvonikDegussa Corporation, under the trade designation Dynasylan® 6498),vinylmethylsiloxane homopolymers, vinylmethylsiloxane copolymers, vinylterminated siloxane homopolymers, and vinyl terminated siloxanecopolymers. However, it is contemplated that a wide range ofpolysiloxanes having vinyl functional groups provide the desired effectsare effective crosslinking agents in accordance with the presentinvention.

Examples of internal silane crosslinkers suitable for the presentinvention are set forth with their chemical structure in Table 1.

TABLE 1 Chemical Chemical Structure Vinyltriisopropenoxy silane

Vinyltriacetoxysilane

Vinyltrimethoxysilane

Vinyltriethoxysilane

Diethoxymethylvinyl silane

Dynasylan ® 6490 (reaction vinyl siloxane oligomer, methoxy functional)

Dynasylan ® 6498 (vinyl siloxane concentrate, oligomeric siloxane,ethoxy functional)

Vinylmethyl polysiloxane

In another embodiment, the superabsorbent polymer may include from about0.001 wt % to about 0.1 wt % based on the total amount of thepolymerizable unsaturated acid group containing monomer of a secondinternal crosslinker which may comprise compositions comprising at leasttwo ethylenically unsaturated double-bonds, for example,methylenebisacrylamide or -methacrylamide or ethylenebisacrylamide;additionally, esters of unsaturated mono- or polycarboxylic acids ofpolyols, such as, diacrylates or triacrylates, e.g., butanediol- orethylene glycol diacrylate or -methacrylate; trimethylolpropanetriacrylate, as well as their alkoxylated derivatives; additionally,allyl compounds, such as allyl (meth)acrylate, triallyl cyanurate,maleic acid diallyl ester, polyallyl ester, tetraallyloxyethane, di- andtriallylamine, tetrallylethylenediamine, allyl esters of phosphoric acidor phosphorous acid. Moreover, compounds having at least one functionalgroup reactive towards acid groups may also be used. Examples thereofinclude N-methylol compounds of amides, such as methacrylamide oracrylamide, and the ethers derived there from, as well as di- andpolyglycidyl compounds.

The present invention further includes from about 0.05 to about 2.0 wt.%, or from about 0.1 to about 1.0 wt %, based on the total amount of thepolymerizable unsaturated acid group containing monomer solution of afoaming agent. The foaming agent may include any alkali metal carbonateor alklali metal bicarbonate containing salt, or mixed salt, sodiumcarbonate, potassium carbonate, ammonium carbonate, magnesium carbonate,or magnesium (hydroxic) carbonates, calcium carbonate, barium carbonate,bicarbonates and hydrates of these, azo compounds or other cations, aswell as naturally occurring carbonates, such as dolomite, or mixturesthereof. Foaming agents may include carbonate salts of multi-valentcations, such as Mg, Ca, Zn, and the like.

Although certain of the multi-valent transition metal cations may beused, some of them, such as ferric cation, can cause color staining andmay be subject to reduction-oxidation reactions or hydrolysis equilibriain water. This may lead to difficulties in quality control of the finalpolymeric product. Also, other multivalent cations, such as Ni, Ba, Cd,Hg would be unacceptable because of potential toxic or skin sensitizingeffects. The foaming agents may include sodium carbonate and sodiumbicarbonate.

The present invention further includes an aqueous solution comprisingfrom about 0.001 to about 1.0 wt. %, or from about 0.002 to about 0.5 wt%, or from about 0.003 to about 0.1 wt %, based on the total amount ofthe polymerizable unsaturated acid group containing monomer solution ofa mixture of a lipophile surfactant and a polyethoxylated hydrophilicsurfactant, wherein the lipophile surfactant may have a HLB of from 4 to9 and the polyethoxylated hydrophilic surfactant has a HLB of from 12 to18; or wherein the lipophile surfactant may be nonionic or thepolyethoxylated hydrophilic surfactant may be nonionic.

Typical examples of the surfactant, polyoxy ethylene alkyl aryl etherssuch as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether,polyoxyethylene stearyl ether, polyoxyethylene oleyl ether,polyoxyethylene alkyl ethers like polyoxyethylene higher alcohol ethers,and polyoxyethylene nonyl phenyl ether; sorbitan fatty esters such assorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate,sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitansesquioleate, and sorbitan distearate; polyoxyethylene sorbitan fattyesters such as polyoxyethylene sorbitan monolaurate, polyoxyethylenesorbitan monolaurate, polyoxyethylene sorbitan monopalmitate,polyoxyethylene sorbitan monostearate, polyoxy-ethylene sorbitantristearate, polyoxyethylene sorbitan mono-oleate, and polyoxyethylenesorbitan trioleate; polyoxyethylene sorbitol fatty esters such astetraoleic acid polyoxyethylene sorbit; glycerin fatty esters such asglycerol monostearate, glycerol monooleate, and self-eumlsifyingglycerol monostearate; polyoxyethylene fatty esters such as polyethyleneglycol mono-laurate, polyethylene glycol monostearate, polyethyleneglycol distearate, and polyethylene glycol monooleate; polyoxyethylenealkyl amines; polyoxyethylene hardened castor oil; and alkyl alcoholamines may be cited. The mixture of nonionic surfactant may include amixture of lipophile surfactant is a sorbitan ester and thepolyethoxylated hydrophilic surfactant is a polyethoxylated sorbitanester.

The usual initiators, such as e.g. azo or peroxo compounds, redoxsystems or UV initiators, (sensitizers), and/or radiation are used forinitiation of the free-radical polymerization. In some aspects,initiators can be used for initiation of the free-radicalpolymerization. Suitable initiators include, but are not limited to, azoor peroxo compounds, redox systems or ultraviolet initiators,sensitizers, and/or radiation.

The polymerization forms a superabsorbent polymer gel, which isgranulated into

superabsorbent polymer particles, or particulate superabsorbent polymer.The superabsorbent polymer gel generally has moisture content of fromabout 40 to 80 wt % of the superabsorbent polymer gel. The reaction timeis not particularly limited, but is only required to be set depending onthe combination of an unsaturated monomer, a crosslinking agent, and aradical polymerization initiator or on such reaction conditions as thereaction temperature.

The particulate superabsorbent polymer generally includes particle sizesranging from about 50 μm to about 1000μ, or from about 150 μm to about850 μm. The present invention may include at least about 40 wt % of theparticles having a particle size from about 300 μm to about 600 μm, atleast about 50 wt % of the particles having a particle size from about300 μm to about 600 μm, or at least about 60 wt % of the particleshaving a particle size from about 300 μm to about 600 μm as measured byscreening through a U.S. standard 30 mesh screen and retained on a U.S.standard 50 mesh screen. In addition, the size distribution of thesuperabsorbent polymer particles of the present invention may includeless than about 30% by weight of particles having a size greater thanabout 600 μm, and less than about 30% by weight of particles having asize of less than about 300 μm, and from 0 to 5 weight % of theparticles less than 150 μm, as measured using for example a RO-TAP®Mechanical Sieve Shaker Model B available from W. S. Tyler, Inc., MentorOhio.

In another embodiment of the particulate superabsorbent polymer of thepresent invention, the diameter of the resin particle is set as follows.The mass average particle diameter is generally from about 200 to about450 μm, or from about 300 to about 430 μm, or from about 300 to about400 μm, or from about 350 to about 400 μm, or from about 360 to about400 μm, or from about 370 to about 400 μm. Further, the percentage ofparticles less than 150 μm is generally from 0 to about 8% by weight, orfrom 0 to about 5% by weight, or from 0 to about 3% by weight, or from 0to about 1% by weight. Further, the percentage of particles more than600 μm is generally from 0 to about 25% by weight, or from 3 to about15% by weight, or from 5 to about 12% by weight, or from 5 to about 8%by weight.

The particle size may be adjusted by subjecting the particles todispersion polymerization and dispersion drying. However, in general,when carrying out aqueous polymerization in particular, the particlesare pulverized and classified after drying, and then mass averagediameter of D50, and the amount of particles smaller than 150 μm andlarger than 600 μm, is adjusted so as to obtain a specific particle sizedistribution. For example, if the specific particle size distribution isachieved by decreasing the diameter of the particles having mass averagediameter of D50 to 400 μm or smaller and also reducing the amount of thefine particles having diameter less than 150 μm and larger than 600 μm,the particles may be first classified into coarse particles and fineparticles after drying by using a general classifying equipment such asa sieve. This process preferably removes coarse particles with adiameter of 5000 μm to 600 μm, or of 2000 μm to 600 μm, or of 1000 μm to600 μm. Then, in the main adjustment process, the fine particles with adiameter less than 150 μm are removed. The removed coarse particles maybe discarded, but they are more likely to be pulverized again throughthe foregoing pulverizing process. The resulting particulatesuperabsorbent polymer thus produced with a specific particle sizedistribution through the pulverizing process is therefore constituted ofirregularly-pulverized particles.

The particulate superabsorbent polymers are surface treated withadditional chemicals and treatments as set forth herein. In particular,the surface of the particulate superabsorbent polymer is crosslinked,generally referred to as surface crosslinking, by the addition of asurface crosslinking agent and heat-treatment. In general, surfacecrosslinking is a process to increase the crosslink density of thepolymer matrix in the vicinity of the particulate superabsorbent polymersurface with respect to the crosslinking density of the particleinterior. The amount of the surface crosslinking agent may be present inan amount of from about 0.01 wt % to about 5 wt % of the dry particulatesuperabsorbent polymer composition, and such as from about 0.1 wt % toabout 3 wt %, and such as from about 0.1 wt % to about 1 wt % by weight,based on the weight of the dry particulate superabsorbent polymercomposition.

Desirable surface crosslinking agents include chemicals with one or morefunctional groups that are reactive toward pendant groups of the polymerchains, typically the acid groups. Surface crosslinker agents comprisefunctional groups which react with functional groups of a polymerstructure in a condensation reaction (condensation crosslinker), in anaddition reaction or in a ring opening reaction. These compounds mayinclude, for example, diethylene glycol, triethylene glycol,polyethylene glycol, glycerine, polyglycerine, propylene glycol,diethanolamine, triethanolamine, polyoxypropylene,oxyethylene-oxypropylene block copolymers, sorbitan fatty acid esters,polyoxyethylene sorbitan fatty acid esters, trimethylolpropane,pentaerythritol, polyvinyl alcohol, oxazolidones such as2-oxazolidinone, N-methyl-2-oxazolidone, Nhydroxyethyl-2-oxazolidone andN-hydroxypropyl-2-oxazolidone, sorbitol, 1,3-dioxolan-2-one (ethylenecarbonate), 4-methyl-1,3-dioxolan-2-one (propylene carbonate), or4,5-dimethyl-1,3-dioxolan-2-one.

After the particulate superabsorbent polymer has been brought intocontact with the surface crosslinker agent, or with the fluid comprisingthe surface crosslinker agent, the treated particulate superabsorbentpolymer is heat treated to a temperature of from about 50 to about 300°C., or from about 75 to about 275° C., or from about 150 to about 250°C., and for a time of from about 5 to about 90 minutes dependent on thetemperature, so that the outer region of the polymer structures is morestrongly crosslinked compared to the inner region (i.e., surfacecrosslinking) The duration of the heat treatment is limited by the riskthat the desired property profile of the polymer structures will bedestroyed as a result of the effect of heat.

In one particular aspect of surface crosslinking, the particulatesuperabsorbent polymer is surface-treated with ethylene carbonatefollowed by heating to affect surface crosslinking of the superabsorbentpolymer particle, which improves the surface crosslinking density andthe gel strength characteristics of the particulate superabsorbentpolymer. More specifically, the surface crosslinking agent is coatedonto the particulate superabsorbent polymer by mixing the particulatesuperabsorbent polymer with an aqueous alcoholic solution of theethylene carbonate surface crosslinking agent. The amount of alcohol inthe aqueous alcoholic solution may be determined by the solubility ofthe alkylene carbonate and is kept as low as possible for variousreasons, for instance, for protection against explosions, and in somecases may be omitted entirely. Suitable alcohols are methanol,isopropanol, ethanol, butanol, or butyl glycol, as well as mixtures ofthese alcohols. In some aspects, the solvent desirably is water, whichtypically is used in an amount of about 0.3% by weight to about 5.0 wt%, based on the weight of the dry particulate superabsorbent polymercomposition. In still other aspects, the ethylene carbonate surfacecrosslinking agent may be applied from a powder mixture, for example,with an inorganic carrier material, such as silicone dioxide (SiO₂), orin a vapor state by sublimation of the ethylene carbonate.

To achieve the desired surface crosslinking properties, the surfacecrosslinking agents such as ethylene carbonate should be distributedevenly on the particulate superabsorbent polymer. For this purpose,mixing is effected in suitable mixers known in the art, such asfluidized bed mixers, paddle mixers, rotary drum mixers, or twin-wormmixers. It is also possible to carry out the coating of the particulatesuperabsorbent polymer during one of the process steps in the productionof the particulate superabsorbent polymer. In one particular aspect, asuitable process for this purpose is the inverse suspensionpolymerization process.

The solution of the surface crosslinking agent may also include a from 0wt % to about 1 wt %, or from about 0.01 wt % to about 0.5 wt % based onthe dry particulate superabsorbent polymer composition of athermoplastic polymer. Examples of thermoplastic polymers includepolyolefin, polyethylene, polyester, linear low density polyethylene(LLDPE), ethylene acrylic acid copolymer (EAA), ethylene alkylmethacrylate copolymer (EMA), polypropylene (PP), maleatedpolypropylene, ethylene vinyl acetate copolymer (EVA), polyester, andblends of all families of polyolefins, such as blends of PP, EVA, EMA,EEA, EBA, HDPE, MDPE, LDPE, LLDPE, and/or VLDPE, may also beadvantageously employed. The term polyolefin as used herein is definedabove. In particular aspects, maleated polypropylene is a preferredthermoplastic polymer for use in the present invention. A thermoplasticpolymer may be functionalized to have additional benefits such as watersolubility or dispersability.

The heat treatment, which follows the coating treatment of theparticulate superabsorbent polymer, may be carried out as follows. Ingeneral, the heat treatment is at a temperature of from about 100° C. toabout 300° C. Lower temperatures are possible if highly reactive epoxidecrosslinking agents are used. However, if an ethylene carbonate is used,then the thermal treatment is suitably at a temperature of from about150° C. to about 250° C. In this particular aspect, the treatmenttemperature depends on the dwell time and the kind of ethylenecarbonate. For example, at a temperature of about 150° C., the thermaltreatment is carried out for one hour or longer. In contrast, at atemperature of about 250° C., a few minutes (e.g., from about 0.5minutes to about 5 minutes) are sufficient to achieve the desiredsurface crosslinking properties. The thermal treatment may be carriedout in conventional dryers or ovens known in the art.

In addition to surface crosslinking, the particulate superabsorbentpolymer compositions may be further surface treated with other chemicalcompositions. The particulate superabsorbent polymer compositionaccording to the invention comprises from about 0.01 wt % to about 5 wt% based on the particulate superabsorbent composition weight of aaluminum salt applied to the surface of the particulate superabsorbentpolymer, in the form of an aqueous solution having a pH value from about5.5 to about 8, or from about 6 to about 7. Or, the particulatesuperabsorbent polymer composition comprises from about 6 wt % to about15 wt % based on the particulate superabsorbent composition weight of anaqueous aluminum salt solution applied to the surface of the surfacecrosslinked particulate superabsorbent polymer, wherein the aqueousaluminum salt solution has a pH value from about 5.5 to about 8, or fromabout 6 to about 7. The aqueous solution of the aluminum salt maycomprise an aluminum cation and a hydroxyl ion or an anion of adeprotonated hydroxyl organic acid. Examples of preferred organic acidsare hydroxyl monocarboxylic acids such as lactic acid, glycolic acid,gluconic acid, or 3-hydroxypropionic acid.

In addition, a superabsorbent polymer composition with significantlyimproved stability including resistance to damage control isunexpectedly obtained by coating the superabsorbent polymer with thealuminum salt solution having adjusted pH of about 5.5 to about 8, orfrom about 6 to about 7, and appropriate concentration and amount. Theaqueous aluminum salt solution includes the reaction product of alkalihydroxide and aluminum sulfate or aluminum sulfate hydrate. In anotherembodiment, the aqueous aluminum salt solution includes the reactionproduct of sodium hydroxide and aluminum sulfate or aluminum sulfatehydrate. In yet another embodiment, the aqueous aluminum salt solutioncomprises an aluminum compound and an organic acid. The mixture of thealuminum compound with the organic acid (salt) can be acidic or basic.And the pH can be adjusted to the desired range with a basic or acidicmaterial. Examples of the basic materials for pH adjustment include butnot limited to sodium hydroxide, potassium hydroxide, ammoniumhydroxide, sodium carbonate or sodium bicarbonate. Examples of theacidic materials for pH adjustment include but are not limited tohydrochloric acid, sulfuric acid, methylsulfonic acid, or carbon dioxidein water. The acidic aluminum salts, such as aluminum chloride, aluminumsulfate, aluminum nitrate and polyaluminum chloride, or the basicaluminum salts, such as sodium aluminate, potassium aluminate andammonium aluminate, may be used for pH adjustment as well.

The aqueous aluminum salt solution may be added at various stages ofsurface treatment of the particulate superabsorbent polymer. In oneembodiment, the aqueous aluminum salt solution may be applied to theparticulate superabsorbent polymer along with the surface crosslinkingsolution.

The aqueous aluminum salt solution may be added after the surfacecrosslinking step, which may be called a post treatment. In oneembodiment, the surface crosslinked particulate superabsorbent polymerand the aluminum salt are mixed using means well known to those skilledin the art. In particular, from about 6 wt % to about 15 wt % of anaqueous aluminum salt solution is applied to a surface crosslinkedparticulate superabsorbent polymer composition.

The particulate superabsorbent polymer composition having improvedstability may include from about 0 wt % to about 5 wt %, or from about0.001 wt % to about 3 wt %, or from about 0.01 wt % to about 2 wt %based on the weight of the dry particulate superabsorbent polymercomposition of a cationic polymer. A cationic polymer as used hereinrefers to a polymer or mixture of polymers comprising a functional groupor groups having a potential of becoming positively charged ions uponionization in an aqueous solution. Suitable functional groups for acationic polymer include, but are not limited to, primary, secondary, ortertiary amino groups, imino groups, imido groups, amido groups, andquaternary ammonium groups. Examples of synthetic cationic polymersinclude the salts or partial salts of poly(vinyl amines),poly(allylamines), or poly(ethylene imine). Examples of natural-basedcationic polymers include partially deacetylated chitin, chitosan, andchitosan salts.

The particulate superabsorbent polymer composition having improvedstability may include from about 0 wt % to about 5 wt %, or from about0.001 wt % to about 3 wt %, or from about 0.01 wt % to about 2 wt %based on the weight of the dry particulate superabsorbent polymercomposition of water-insoluble, inorganic powder. Examples of insoluble,inorganic powders include silicon dioxide, silica, titanium dioxide,aluminum oxide, magnesium oxide, zinc oxide, talc, calcium phosphate,clays, diatomaceous earth, zeolites, bentonite, kaolin, hydrotalcite,activated clays, etc. The insoluble inorganic powder additive may be asingle compound or a mixture of compounds selected from the above list.Examples of silica include fumed silica, precipitated silica, silicondioxide, silicic acid, and silicates. In some particular aspects,microscopic noncrystalline silicon dioxide is desirable. Productsinclude SIPERNAT® 22S and AEROSIL® 200 available from EvonikCorporation, Parsippany, N.J. In some aspects, the particle diameter ofthe inorganic powder can be 1,000 μm or smaller, such as 100 μm orsmaller.

The particulate superabsorbent polymer composition having improvedstability may also include from 0 wt % to about 30 wt %, or from about0.001 wt % to about 25 wt %, or from about 0.01 wt % to about 20 wt %based on the weight of the dry particulate superabsorbent polymercomposition, of water-soluble polymers, such as partly or completelyhydrolyzed polyvinyl acetate, polyvinylpyrrolidone, starch or starchderivatives, polyglycols or polyacrylic acids, preferably inpolymerized-in form. The molecular weight of these polymers is notcritical as long as they are water-soluble. Preferred water-solublepolymers are starch and polyvinyl alcohol. The preferred content of suchwater-soluble polymers in the absorbent polymer according to theinvention is 0-30 wt %, or 0-5 wt %, based on the total amount of thedry particulate superabsorbent polymer composition. The water-solublepolymers, preferably synthetic polymers, such as polyvinyl alcohol, canalso serve as a graft base for the monomers to be polymerized.

The particulate superabsorbent polymer composition having improvedstability may also include from 0 wt % to about 5 wt %, or from about0.001 wt % to about 3 wt %, or from about 0.01 wt % to about 2 wt %based on the weight of the dry particulate superabsorbent polymercomposition, of dedusting agents, such as hydrophilic and hydrophobicdedusting agents such as those described in U.S. Pat. Nos. 6,090,875 and5,994,440.

In some aspects, additional surface additives may optionally be employedwith the particulate superabsorbent polymer composition having improvedpermeability stability, such as odor-binding substances, such ascyclodextrins, zeolites, inorganic or organic salts, and similarmaterials; anti-caking additives, flow modification agents, surfactants,viscosity modifiers, and the like.

The particulate superabsorbent polymer composition having improvedstability of the present invention may be, after the heat treatmentstep, treated with an aqueous solution, such as the aqueous solution ofdeprotonated organic acid salt, aluminum salt, or water soluble polymersuch as polyethylene glycol. The treated particulate superabsorbentpolymer composition has moisture content of from about 3 wt % to about15 wt %, or from about 4 wt % to about 12 wt %, or from 5 wt % to about11 wt % based on the particulate superabsorbent polymer composition.

The particulate superabsorbent polymer composition having improvedstability according to the invention may be desirably prepared byvarious methods disclosed in the art including the following methods andexemplified in the Examples. The particulate superabsorbent polymercomposition may be prepared continuously or discontinuously in alarge-scale industrial manner, the post treatment being carried outaccording to the invention.

According to one method, the monomer is partially neutralized by eitheradding an alkali base such as sodium hydroxide to the monomer or byadding the monomer to an alkali base solution. Then the partiallyneutralized monomer, such as acrylic acid, is converted into a gel byfree-radical polymerization in aqueous solution in the presence ofcrosslinking agents and any further components, and the gel iscomminuted, dried, ground, and sieved off to the desired particle size,thereby forming a particulate superabsorbent polymer. Thispolymerization can be carried out continuously or discontinuously.

For the present invention, the size of the high-capacity superabsorbentpolymer composition particles is dependent on manufacturing processesincluding milling and sieving. It is well known to those skilled in theart that particle size distribution of the particulate superabsorbentpolymer resembles a normal distribution or a bell shaped curve. It isalso known that for various reasons, the normal distribution of theparticle size distribution may be skewed in either direction.

According to another method to make particulate superabsorbent polymer,inverse suspension and emulsion polymerization can also be used forpreparation of the products according to the invention. According tothese processes, an aqueous, partly neutralized solution of monomer,such as acrylic acid, is dispersed in a hydrophobic, organic solventwith the aid of protective colloids and/or emulsifiers, and thepolymerization is started by free radical initiators. The internalcrosslinking agents may be either dissolved in the monomer solution andare metered in together with this, or are added separately andoptionally during the polymerization. The addition of a water-solublepolymer as the graft base optionally takes place via the monomersolution or by direct introduction into the oily phase. The water isthen removed azeotropically from the mixture, and the polymer isfiltered off and optionally dried. Internal crosslinking can be carriedout by polymerizing-in a polyfunctional crosslinking agent dissolved inthe monomer solution and/or by reaction of suitable crosslinking agentswith functional groups of the polymer during the polymerization steps.

The particulate superabsorbent polymer composition having improvedstability of the present invention exhibits certain characteristics, orproperties, as measured by Free Swell Gel Bed Permeability (FSGBP),Centrifuge Retention Capacity (CRC), absorbency under load at about 0.9psi (0.9 psi AUL) and Compressibility. The FSGBP Test is a measurementof the permeability of a swollen bed of particulate superabsorbentpolymer composition in terms of 10-8 cm2 (e.g., separate from theabsorbent structure) under a confining pressure after what is commonlyreferred to as “free swell” conditions. In this context, the term “freeswell” means that the particulate superabsorbent polymer composition isallowed to swell without a swell restraining load upon absorbing testsolution as will be described.

Permeability is a measure of the effective connectedness of a porousstructure, be it a mat of fiber or a slab of foam or, in the case ofthis application, particulate superabsorbent polymer and particulatesuperabsorbent polymer composition, generally referred to as particulatesuperabsorbent polymer compositions herein, or SAP, and may be specifiedin terms of the void fraction and extent of connectedness of theparticulate superabsorbent polymer compositions. Gel permeability is aproperty of the mass of particulate superabsorbent polymer compositionsas a whole and is related to particle size distribution, particle shape,the connectedness of the open pores, shear modulus and surfacemodification of the swollen gel. In practical terms, the permeability ofthe particulate superabsorbent polymer composition is a measure of howrapidly liquid flows through the mass of swollen particles. Lowpermeability indicates that liquid cannot flow readily through theparticulate superabsorbent polymer compositions, which is generallyreferred to as gel blocking, and that any forced flow of liquid (such asa second application of urine during use of the diaper) must take analternate path (e.g., diaper leakage).

The Centrifuge Retention Capacity (CRC) Test measures the ability of theparticulate superabsorbent polymer composition to retain liquid thereinafter being saturated and subjected to centrifugation under controlledconditions. The resultant retention capacity is stated as grams ofliquid retained per gram weight of the sample (g/g).

The Absorbency Under Load (AUL) Test measures the ability of theparticulate superabsorbent polymer composition particles to absorb a 0.9weight percent solution of sodium chloride in distilled water at roomtemperature (test solution) while the material is under a load of 0.9psi.

The Compressibility Test measures the relative volume change of theparticulate superabsorbent polymer composition as a response to apressure change and is performed on original particulate superabsorbentpolymer composition, or shortly after the particulate superabsorbentpolymer composition is manufactured.

The Processing Test measures the stability of performance properties ofthe particulate superabsorbent polymer composition against externalforces applied to the particulate superabsorbent polymer compositionprior to or subsequent to the application of the Processing Test. Thetest conditions are selected to simulate the debulking process ofabsorbent articles.

All values of Centrifuge Retention Capacity, Absorbency Under Load andGel Bed Permeability set forth herein are to be understood as beingdetermined by the Centrifuge Retention Capacity Test, Absorbency UnderLoad Test, Free Swell Gel Bed Permeability Test and Compressibility Testas provided herein.

The particulate superabsorbent polymer composition having improvedstability made by a process of the present invention may have acentrifuge retention capacity of from about 25 g/g to about 40 g/g, orfrom about 27 to about 35 g/g; and an absorbency under load at 0.9 psiprior to subjecting the treated particulate superabsorbent polymercomposition to the Processing Test of from about 15 g/g to about 21 g/g,or from about 16 g/g to about 20 g/g; an absorbency under load at 0.9psi subsequent to subjecting the particulate superabsorbent polymercomposition to the Processing Test of from about 14 g/g to about 21 g/g,or from about 14 g/g to about 20 g/g; a compressibility of from about1.30 mm²/N to about 4 mm²/N, or from about 1.30 mm²/N to about 3.5mm²/N, a permeability stability index of from about 0.60 to about 0.99,or from about 0.70 to about 0.97, and an original Free Swell Gel BedPermeability (FSGBP) of about 30×10⁻⁸ cm² to about 200×10⁻⁸ cm² prior tosubjecting the treated particulate superabsorbent polymer composition toa Processing Test, the particulate superabsorbent polymer compositionhas a permeability stability index of from about 0.60 to about 0.99, orfrom about 0.70 to about 0.97. In addition, the particulatesuperabsorbent polymer composition has an absorbency against pressure(AAP) of 4.8 kPa for the physiological saline solution being not morethan 21 g/g, or from 15 g/g to 20 g/g. In addition, the particulatesuperabsorbent polymer composition having improved stability may have acentrifuge retention capacity increase of at least 2 g/g, or from 2 g/gto about 50 g/g, or from 2 g/g to about 30 g/g.

The particulate superabsorbent polymer composition according to thepresent invention generally has a particle size of from about 150 μm toabout 850 μm and comprises from about 1 to about 40 wt % of theparticulate superabsorbent polymer composition having a particle size ofmore than 600 μm or from about 1 to about 35 wt % of the particulatesuperabsorbent polymer composition having a particle size of more than600 μm, or from about 12 wt % to about 25 wt % of the particulatesuperabsorbent polymer composition having a particle size of more than600 μm, or less than about 15 wt % of the particulate superabsorbentpolymer composition having a particle size of more than 600 μm and asspecified by the standard sieve classification. In addition, theparticulate superabsorbent polymer composition according to the presentinvention may have a weight average particle diameter (D50) as specifiedby standard sieve classification of from about 300 to about 400 μm, orfrom about 350 to about 400 μm, or from about 360 to about 400 μm, orfrom about 370 to about 400 μm.

The particulate superabsorbent polymer compositions according to thepresent invention can be employed in many absorbent articles includingsanitary towels, diapers, or wound coverings, and they have the propertythat they rapidly absorb large amounts of menstrual blood, urine, orother body fluids. Since the agents according to the invention retainthe absorbed liquids even under pressure and are also capable ofdistributing further liquid within the construction in the swollenstate, they are more desirably employed in higher concentrations, withrespect to the hydrophilic fiber material, such as fluff, when comparedto conventional current superabsorbent compositions. They are alsosuitable for use as a homogeneous superabsorber layer without fluffcontent within the diaper construction, as a result of whichparticularly thin articles are possible. The polymers are furthermoresuitable for use in hygiene articles (e.g., incontinence products) foradults.

The polymers according to the invention are also employed in absorbentarticles that are suitable for further uses. In particular, the polymersof this invention can be used in absorbent compositions for absorbentsfor water or aqueous liquids, preferably in constructions for absorptionof body fluids, in foamed and non-foamed sheet-like structures, inpackaging materials, in constructions for plant growing, as soilimprovement agents or as active compound carriers. For this, they areprocessed to a web by mixing with paper or fluff or synthetic fibers orby distributing the superabsorbent polymers between substrates of paper,fluff or non-woven textiles or by processing into carrier materials.

Test Procedures

It is noted that all property measurements are done before theProcessing Test unless otherwise specified.

The Vortex Test

The Vortex Test measures the amount of time in seconds required for 2grams of a SAP to close a vortex created by stirring 50 milliliters ofsaline solution at 600 revolutions per minute on a magnetic stir plate.The time it takes for the vortex to close is an indication of the freeswell absorbing rate of the SAP.

Equipment and materials1. Schott Duran 100 ml Beaker and 50 ml graduated cylinder.2. Programmable magnetic stir plate, capable of providing 600revolutions per minute (such as that commercially available from PMCIndustries, under the trade designation Dataplate® Model #721).3. Magnetic stir bar without rings, 7.9 millimeters.times.32millimeters, Teflon® covered (such as that commercially available fromBaxter Diagnostics, under the trade designation S/PRIM. brand singlepack round stirring bars with removable pivot ring).

4. Stopwatch

5. Balance, accurate to +/−0.01 g6. Saline solution, 0.87 w/w % Blood Bank Saline available from BaxterDiagnostics (considered, for the purposes of this application to be theequivalent of 0.9 wt. % saline7. Weighing paper8. Room with standard condition atmosphere: Temp=23° C.+/−1° C. andRelative Humidity=50%+/−2%.

Test Procedure

1. Measure 50 ml+/−0.01 ml of saline solution into the 100 ml beaker.2. Place the magnetic stir bar into the beaker.3. Program the magnetic stir plate to 600 revolutions per minute.4. Place the beaker on the center of the magnetic stir plate such thatthe magnetic stir bar is activated. The bottom of the vortex should benear the top of the stir bar.5. Weigh out 2 g+/−0.01 g of the SAP to be tested on weighing paper.NOTE: The SAP is tested as received (i.e. as it would go into anabsorbent composite such as those described herein). No screening to aspecific particle size is done, though the particle size is known tohave an effect on this test.6. While the saline solution is being stirred, quickly pour the SAP tobe tested into the saline solution and start the stopwatch. The SAP tobe tested should be added to the saline solution between the center ofthe vortex and the side of the beaker.7. Stop the stopwatch when the surface of the saline solution becomesflat and record the time.8. The time, recorded in seconds, is reported as the Vortex Time.

Centrifuge Retention Capacity Test (CRC)

The CRC Test measures the ability of the particulate superabsorbentpolymer composition to retain liquid therein after being saturated andsubjected to centrifugation under controlled conditions. The resultantretention capacity is stated as grams of liquid retained per gram weightof the sample, (g/g). The CRC Test can be performed either before orafter subjecting the particulate superabsorbent polymer composition to aProcessing Test, as set forth herein. The sample to be tested isprepared from particles that are pre-screened through a U.S. standard30-mesh screen and retained on a U.S. standard 50-mesh screen. As aresult, the particulate superabsorbent polymer composition samplecomprises particles sized in the range of about 300 to about 600microns. The particles can be pre-screened by hand or automatically.

The retention capacity is measured by placing about 0.20 grams of thepre-screened particulate superabsorbent polymer composition sample intoa water-permeable bag that will contain the sample while allowing a testsolution (0.9 weight percent sodium chloride in distilled water) to befreely absorbed by the sample. A heat-sealable tea bag material, such asthat available from Dexter Corporation (having a place of business inWindsor Locks, Conn., U.S.A.) as model designation 1234T heat sealablefilter paper works well for most applications. The bag is formed byfolding a 5-inch by 3-inch sample of the bag material in half andheat-sealing two of the open edges to form a 2.5-inch by 3-inchrectangular pouch. The heat seals are about 0.25 inches inside the edgeof the material. After the sample is placed in the pouch, the remainingopen edge of the pouch is also heat-sealed. Empty bags are also made toserve as controls. Three samples are prepared for each particulatesuperabsorbent polymer composition to be tested.

The sealed bags are submerged in a pan containing the test solution atabout 23° C., making sure that the bags are held down until they arecompletely wetted. After wetting, the particulate superabsorbent polymercomposition samples remain in the solution for about 30 minutes, atwhich time they are removed from the solution and temporarily laid on anon-absorbent flat surface.

The wet bags are then placed into the basket wherein the wet bags areseparated from each other and are placed at the outer circumferentialedge of the basket, wherein the basket is of a suitable centrifugecapable of subjecting the samples to a g-force of about 350. Onesuitable centrifuge is a CLAY ADAMS DYNAC II, model #0103, having awater collection basket, a digital rpm gauge, and a machined drainagebasket adapted to hold and drain the flat bag samples. Where multiplesamples are centrifuged, the samples are placed in opposing positionswithin the centrifuge to balance the basket when spinning. The bags(including the wet, empty bags) are centrifuged at about 1,600 rpm(e.g., to achieve a target g-force of about 350 g force with a variancefrom about 240 to about 360 g force), for 3 minutes. G force is definedas an unit of inertial force on a body that is subjected to rapidacceleration or gravity, equal to 32 ft/sec² at sea level. The bags areremoved and weighed, with the empty bags (controls) being weighed first,followed by the bags containing the particulate superabsorbent polymercomposition samples. The amount of solution retained by the particulatesuperabsorbent polymer composition sample, taking into account thesolution retained by the bag itself, is the centrifuge retentioncapacity (CRC) of the superabsorbent polymer, expressed as grams offluid per gram of superabsorbent polymer. More particularly, theretention capacity is determined by the following equation:

CRC=[sample bag after centrifuge−empty bag after centrifuge−dry sampleweight]/dry sample weight

The three samples are tested, and the results are averaged to determinethe CRC of the particulate superabsorbent polymer composition.

CRC(rt, 0.5 hr) is measured with a testing temperature of about 23° C.(room temperature) and a testing time of 0.5 hour.

CRC(bt, 5 hr) is measured with a testing temperature of about 37° C.(body temperature) and a testing time of 5 hours.

Centrifuge Retention Capacity Increase (CRCI) Test

The Centrifuge Retention Capacity Increase (CRCI) Test measures theincrease in the CRC that occurs and is calculated as the differencebetween the second CRC Test and the first CRC(rt,0.5 hr) Test and isdetermined by the following equation:

CRC Increase=CRC(bt,5 hr).−(CRC(rt,0.5 hr).

Free-Swell Gel Bed Permeability Test (FSGBP)

As used herein, the Free-Swell Gel Bed Permeability Test, also referredto as the Gel Bed Permeability Under 0 psi Swell Pressure Test (FSGBP),determines the permeability of a swollen bed of gel particles (e.g.,such as the particulate superabsorbent polymer composition, or theparticulate superabsorbent polymer prior to being surface treated),under what is commonly referred to as “free swell” conditions. The term“free swell” means that the gel particles are allowed to swell without arestraining load upon absorbing test solution as will be described. Asuitable apparatus for conducting the Gel Bed Permeability Test is shownin FIGS. 1, 2, and 3 and indicated generally as 500. The test apparatusassembly 528 comprises a sample container, generally indicated at 530,and a plunger, generally indicated at 536. The plunger comprises a shaft538 having a cylinder hole bored down the longitudinal axis and a head550 positioned at the bottom of the shaft. The shaft hole 562 has adiameter of about 16 mm. The plunger head is attached to the shaft, suchas by adhesion. Twelve holes 544 are bored into the radial axis of theshaft, three positioned at every 90 degrees having diameters of about6.4 mm. The shaft 538 is machined from a LEXAN rod or equivalentmaterial and has an outer diameter of about 2.2 cm and an inner diameterof about 16 mm.

The plunger head 550 has a concentric inner ring of seven holes 560 andan outer ring of 14 holes 554, all holes having a diameter of about 8.8millimeters as well as a hole of about 16 mm aligned with the shaft. Theplunger head 550 is machined from a LEXAN rod or equivalent material andhas a height of approximately 16 mm and a diameter sized such that itfits within the cylinder 534 with minimum wall clearance but stillslides freely. The total length of the plunger head 550 and shaft 538 isabout 8.25 cm, but can be machined at the top of the shaft to obtain thedesired mass of the plunger 536. The plunger 536 comprises a 100 meshstainless steel cloth screen 564 that is biaxially stretched to tautnessand attached to the lower end of the plunger 536. The screen is attachedto the plunger head 550 using an appropriate solvent that causes thescreen to be securely adhered to the plunger head 550. Care must betaken to avoid excess solvent migrating into the open portions of thescreen and reducing the open area for liquid flow. Acrylic adhesive,Weld-On #4, from IPS Corporation (having a place of business in Gardena,Calif., USA) is a suitable adhesive.

The sample container 530 comprises a cylinder 534 and a 400 meshstainless steel cloth screen 566 that is biaxially stretched to tautnessand attached to the lower end of the cylinder 534. The screen isattached to the cylinder using an appropriate solvent that causes thescreen to be securely adhered to the cylinder. Care must be taken toavoid excess solvent migrating into the open portions of the screen andreducing the open area for liquid flow. Acrylic adhesive, Weld-On #4,from IPS Corporation is a suitable adhesive. A gel particle sample,indicated as 568 in FIG. 2, is supported on the screen 566 within thecylinder 534 during testing.

The cylinder 534 may be bored from a transparent LEXAN rod or equivalentmaterial, or it may be cut from a LEXAN tubing or equivalent material,and has an inner diameter of about 6 cm (e.g., a cross-sectional area ofabout 28.27 cm²), a wall thickness of about 0.5 cm and a height ofapproximately 7.95 cm. A step is machined into the outer diameter of thecylinder 534 such that a region 534 a with an outer diameter of 66 mmexists for the bottom 31 mm of the cylinder 534. An o-ring 540 whichfits the diameter of region 534 a may be placed at the top of the step.

The annular weight 548 has a counter-bored hole about 2.2 cm in diameterand 1.3 cm deep so that it slips freely onto the shaft 538. The annularweight also has a thrubore 548 a of about 16 mm. The annular weight 548can be made from stainless steel or from other suitable materialsresistant to corrosion in the presence of the test solution, which is0.9 weight percent sodium chloride solution in distilled water. Thecombined weight of the plunger 536 and annular weight 548 equalsapproximately 596 grams (g), which corresponds to a pressure applied tothe sample 568 of about 0.3 pounds per square inch (psi), or about 20.7dynes/cm2 (2.07 kPa), over a sample area of about 28.27 cm².

When the test solution flows through the test apparatus during testingas described below, the sample container 530 generally rests on a weir600. The purpose of the weir is to divert liquid that overflows the topof the sample container 530 and diverts the overflow liquid to aseparate collection device 601. The weir can be positioned above a scale602 with a beaker 603 resting on it to collect saline solution passingthrough the swollen sample 568.

To conduct the Gel Bed Permeability Test under “free swell” conditions,the plunger 536, with the weight 548 seated thereon, is placed in anempty sample container 530 and the height from the top of the weight 548to the bottom of the sample container 530 is measured using a suitablegauge accurate to 0.01 mm. The force the thickness gauge applies duringmeasurement should be as low as possible, preferably less than about0.74 Newtons. It is important to measure the height of each empty samplecontainer 530, plunger 536, and weight 548 combination and to keep trackof which plunger 536 and weight 548 is used when using multiple testapparatus. The same plunger 536 and weight 548 should be used formeasurement when the sample 568 is later swollen following saturation.It is also desirable that the base that the sample cup 530 is resting onis level, and the top surface of the weight 548 is parallel to thebottom surface of the sample cup 530.

The sample to be tested is prepared from the particulate superabsorbentpolymer composition, which is prescreened through a U.S. standard 30mesh screen and retained on a U.S. standard 50 mesh screen. As a result,the test sample comprises particles sized in the range of about 300 toabout 600 microns. The superabsorbent polymer particles can bepre-screened with, for example, a RO-TAP Mechanical Sieve Shaker Model Bavailable from W. S. Tyler, Inc., Mentor Ohio. Sieving is conducted for10 minutes. Approximately 2.0 grams of the sample is placed in thesample container 530 and spread out evenly on the bottom of the samplecontainer. The container, with 2.0 grams of sample in it, without theplunger 536 and weight 548 therein, is then submerged in the 0.9% salinesolution for a time period of about 60 minutes to saturate the sampleand allow the sample to swell free of any restraining load. Duringsaturation, the sample cup 530 is set on a mesh located in the liquidreservoir so that the sample cup 530 is raised slightly above the bottomof the liquid reservoir. The mesh does not inhibit the flow of salinesolution into the sample cup 530. A suitable mesh can be obtained aspart number 7308 from Eagle Supply and Plastic, having a place ofbusiness in Appleton, Wis., U.S.A. Saline does not fully cover thesuperabsorbent polymer composition particles, as would be evidenced by aperfectly flat saline surface in the test cell. Also, saline depth isnot allowed to fall so low that the surface within the cell is definedsolely by swollen superabsorbent, rather than saline.

At the end of this period, the plunger 536 and weight 548 assembly isplaced on the saturated sample 568 in the sample container 530 and thenthe sample container 530, plunger 536, weight 548, and sample 568 areremoved from the solution. After removal and before being measured, thesample container 530, plunger 536, weight 548, and sample 568 are toremain at rest for about 30 seconds on a suitable flat, large gridnon-deformable plate of uniform thickness. The thickness of thesaturated sample 568 is determined by again measuring the height fromthe top of the weight 548 to the bottom of the sample container 530,using the same thickness gauge used previously provided that the zeropoint is unchanged from the initial height measurement. The samplecontainer 530, plunger 536, weight 548, and sample 568 may be placed ona flat, large grid nondeformable plate of uniform thickness that willprovide for drainage. The plate has an overall dimension of 7.6 cm by7.6 cm, and each grid has a cell size dimension of 1.59 cm long by 1.59cm wide by 1.12 cm deep. A suitable flat, large grid non-deformableplate material is a parabolic diffuser panel, catalogue number 1624K27,available from McMaster Carr Supply Company, having a place of businessin Chicago, Ill., U.S.A., which can then be cut to the properdimensions. This flat, large mesh non-deformable plate must also bepresent when measuring the height of the initial empty assembly. Theheight measurement should be made as soon as practicable after thethickness gauge is engaged. The height measurement obtained frommeasuring the empty sample container 530, plunger 536, and weight 548 issubtracted from the height measurement obtained after saturating thesample 568. The resulting value is the thickness, or height “H” of theswollen sample.

The permeability measurement is initiated by delivering a flow of the0.9% saline solution into the sample container 530 with the saturatedsample 568, plunger 536, and weight 548 inside. The flow rate of testsolution into the container is adjusted to cause saline solution tooverflow the top of the cylinder 534 thereby resulting in a consistenthead pressure equal to the height of the sample container 530. The testsolution may be added by any suitable means that is sufficient to ensurea small, but consistent amount of overflow from the top of the cylinder,such as with a metering pump 604. The overflow liquid is diverted into aseparate collection device 601. The quantity of solution passing throughthe sample 568 versus time is measured gravimetrically using the scale602 and beaker 603. Data points from the scale 602 are collected everysecond for at least sixty seconds once the overflow has begun. Datacollection may be taken manually or with data collection software. Theflow rate, Q, through the swollen sample 568 is determined in units ofgrams/second (g/s) by a linear least-square fit of fluid passing throughthe sample 568 (in grams) versus time (in seconds).

Permeability in cm² is obtained by the following equation:

K=[Q*H*μ]/[A*p*P]

where K=Permeability (cm²), Q=flow rate (g/sec), H=height of swollensample (cm), n=liquid viscosity (poise) (approximately one centipoisefor the test solution used with this Test), A=cross-sectional area forliquid flow (28.27 cm2 for the sample container used with this Test),p=liquid density (g/cm³) (approximately one g/cm³, for the test solutionused with this Test) and P=hydrostatic pressure (dynes/cm²) (normallyapproximately 7,797 dynes/cm²). The hydrostatic pressure is calculatedfrom P=p*g*h, where p=liquid density (g/cm³), g=gravitationalacceleration, nominally 981 cm/sec², and h=fluid height, e.g., 7.95 cmfor the Gel Bed Permeability Test described herein.

A minimum of two samples is tested and the results are averaged todetermine the gel bed permeability of the sample of particulatesuperabsorbent polymer composition.

The FSGBP can be measured as described herein prior to subjecting aparticulate superabsorbent polymer composition to a Processing Test asdescribed herein. Such a FSGBP value can be referred to as the“original” FSGBP of the particulate superabsorbent polymer composition.The FSGBP may also be measured subsequent to subjecting the particulatesuperabsorbent polymer composition to the Processing Test. Such a FSGBPvalue can be referred to as the “post processing” FSGBP. Comparing theoriginal FSGBP of a particulate superabsorbent polymer composition withthe post processing FSGBP of the particulate superabsorbent polymercomposition can be used as a measure of the stability of thecomposition. It should be noted that all “original” and “postprocessing” FSGBP values reported herein were measured using a sample ofpre-screened 300 to 600 μm particles.

Absorbency Under Load Test (AUL(0.9 Psi))

The Absorbency Under Load (AUL) Test measures the ability of theparticulate superabsorbent polymer composition to absorb a 0.9 weightpercent solution of sodium chloride in distilled water at roomtemperature (test solution) while the material is under a 0.9 psi load.The apparatus for testing AUL consists of:

-   -   An AUL assembly including a cylinder, a 4.4 g piston, and a        standard 317 gm weight. The components of this assembly are        described in additional detail below.    -   A flat-bottomed square plastic tray that is sufficiently broad        to allow the glass frits to lay on the bottom without contact        with the tray walls. A plastic tray that is 9″ by 9″(22.9        cm×22.9 cm), with a depth of 0.5 to 1″(1.3 cm to 2.5 cm) is        commonly used for this test method.    -   A 9 cm diameter sintered glass frit with a ‘C’ porosity (25-50        microns). This frit is prepared in advance through equilibration        in saline (0.9% sodium chloride in distilled water, by weight).        In addition to being washed with at least two portions of fresh        saline, the frit must be immersed in saline for at least 12        hours prior to AUL measurements.    -   Whatman Grade 1, 9 cm diameter filter paper circles.    -   A supply of saline (0.9% sodium chloride in distilled water, by        weight).

Referring to FIG. 4, the cylinder 412 of the AUL assembly 400 used tocontain the particulate superabsorbent polymer composition 410 is madefrom one-inch (2.54 cm) inside diameter thermoplastic tubingmachined-out slightly to be sure of concentricity. After machining, a400 mesh stainless steel wire cloth 414 is attached to the bottom of thecylinder 412 by heating the steel wire cloth 414 in a flame until redhot, after which the cylinder 412 is held onto the steel wire clothuntil cooled. A soldering iron can be utilized to touch up the seal ifunsuccessful or if it breaks. Care must be taken to maintain a flatsmooth bottom and not distort the inside of the cylinder 412.

The 4.4 g piston (416) is made from one-inch diameter solid material(e.g., PLEXIGLAS®) and is machined to closely fit without binding in thecylinder 412.

A standard 317 gm weight 418 is used to provide a 62,053 dyne/cm2 (about0.9 psi) restraining load. The weight is a cylindrical, 1 inch (2.5 cm)diameter, stainless steel weight that is machined to closely fit withoutbinding in the cylinder.

Unless specified otherwise, a sample 410 corresponding to a layer of atleast about 300 gsm. (0.16 g) of superabsorbent polymer compositionparticles is utilized for testing the AUL. The sample 410 is taken fromsuperabsorbent polymer composition particles that are pre-screenedthrough U.S. standard #30 mesh and retained on U.S. std. #50 mesh. Thesuperabsorbent polymer composition particles can be pre-screened with,for example, a RO-TAP® Mechanical Sieve Shaker Model B available from W.S. Tyler, Inc., Mentor Ohio. Sieving is conducted for about 10 minutes.

The inside of the cylinder 412 is wiped with an antistatic cloth priorto placing the superabsorbent polymer composition particles 410 into thecylinder 412.

The desired amount of the sample of sieved particulate superabsorbentpolymer composition 410 (about 0.16 g) is weighed out on a weigh paperand evenly distributed on the wire cloth 414 at the bottom of thecylinder 412. The weight of the particulate superabsorbent polymercomposition in the bottom of the cylinder is recorded as ‘SA,’ for usein the AUL calculation described below. Care is taken to be sure noparticulate superabsorbent polymer composition cling to the wall of thecylinder. After carefully placing the 4.4 g piston 412 and 317 g weight418 on the superabsorbent polymer composition particles 410 in thecylinder 412, the AUL assembly 400 including the cylinder, piston,weight, and particulate superabsorbent polymer composition particles isweighed, and the weight is recorded as weight ‘A’.

A sintered glass frit 424 (described above) is placed in the plastictray 420, with saline 422 added to a level equal to that of the uppersurface of the glass frit 424. A single circle of filter paper 426 isplaced gently on the glass frit 424, and the AUL assembly 400 with theparticulate superabsorbent polymer composition 410 is then placed on topof the filter paper 426. The AUL assembly 400 is then allowed to remainon top of the filter paper 426 for a test period of one hour, withattention paid to keeping the saline level in the tray constant. At theend of the one hour test period, the AUL apparatus is then weighed, withthis value recorded as weight ‘B.’

The AUL(0.9 psi) is calculated as follows:

AUL(0.9 psi)=(B−A)/SA

wherein

A=Weight of AUL Unit with dry SAP

B=Weight of AUL Unit with SAP after 60 minutes absorption

SA=Actual SAP weight

A minimum of two tests is performed and the results are averaged todetermine the AUL value under 0.9 psi load. The particulatesuperabsorbent polymer composition samples are tested at about 23° C.and about 50% relative humidity.

Absorbency Against Pressure [AAP(0.7 psi)]

A stainless-steel 400-mesh standard sieve (mesh size of 38 μm) was fusedon the bottom of a plastic support cylinder having an inner diameter of60 mm, and 0.9000 g of water absorbent resin or water absorbent wasuniformly sprinkled on the sieve. A piston with an outer diameterslightly smaller than 60 mm, sized to fit inside the support cylinderwith no clearance but with a free vertical stroke within the cylinderwas prepared. The piston was adjusted in such a manner that a load of4.83 kPa (0.7 psi) could be uniformly applied on the water absorbentresin or water absorbent. The piston and the load were placed in thisorder on the water absorbent resin or water absorbent, and the totalmass Wa (g) of this measuring device was measured. Then, a glass filterhaving a diameter of 90 mm (made by Sougo Rikagaku Garasu SeisakushoCo., Ltd.; pore diameter of 100 μm to 120 μm) was placed inside a Petridish having a diameter of 150 mm, and each solution was added to thelevel of the upper surface of the glass filter.

On the glass filter, a piece of filter paper, Whatman Grade 1, 9 cmdiameter filter paper circles was placed to completely wet the filterpaper, and an excess solution was removed.

The measuring device was then placed on the wet filter paper to absorbthe contacted solution under pressure. After 1 hour, the measuringdevice was lifted and a weight Wb (g) of the measuring device wasmeasured. From the values of W a and Wb so measured, an absorbencyagainst pressure (g/g) was calculated using the following formula:

AAP(0.7)(g/g)=(Wb(g)−Wa(g))/(0.9 g of water absorbent resin)

Moisture Content Test

The amount of water content, measured as “% moisture,” can be measuredas follows: 1) Weigh 5.0 grams of superabsorbent polymer composition(SAP) accurately in a pre-weighed aluminum weighing pan; 2) place theSAP and pan into a standard lab oven preheated to 105° C. for 3 hours;3) remove and re-weigh the pan and contents; and 4) calculate thepercent moisture using the following formula:

% Moisture={((pan wt+initial SAP wt)−(dried SAP & pan wt))*100}/initialSAP wt

Compressibility Test

The compressibility test measures the relative volume change of theparticulate superabsorbent polymer composition as a response to apressure change. The test is conducted on a Zwick Tensile/CompressionTester Zwicki 1120. A sample of the superabsorbent polymer compositionis placed in a testing cell of a thick-walled cylinder closed at thebottom and fitted at the top with a movable piston. The cylinder is 50mm in diameter and 1 cm in depth. The piston moves at a speed of 0.2mm/min. The normal force starts to increase when the piston touches thesurface of the sample. The test is completed when the normal forcereaches 90 N. The sample heights at the normal forces of ON and 90N arerecorded automatically by the computer that is hooked to the ZwickTensile/Compression Tester.

Compressibility=(initial height−final height)/(initial height)×(surfacearea of piston)/(maximum normal force)

Processing Test

The processing test measures the stability of performance properties ofthe superabsorbent polymer composition against external forces. The testconditions are selected to simulate the debulking process of absorbentarticles. 40 grams of a sample of a particulate superabsorbent polymercomposition is distributed through an eight inch US standard 18 meshscreen onto a piece of chipboard (dimension 22.5″×17.25″×0.03″,commercially available from Central Wisconsin Paper which is located inWausau, Wis., USA) to form an eight inch diameter circle. Another pieceof chipboard is then placed over the sample to formachipboard-sample-chipboard sandwich. The sandwich is then put through atwo roll calendar press (BF Perkins serial number H8617-67) set at 1150pounds per square inch of hydraulic pressure and a speed of 20 rpm. Theprocessed sample is then removed from the chipboard. The CRC, AUL andFSGBP are then determined for the original and processed samples. Thepermeability stability index is used as the indicator of the stabilityof the superabsorbent polymer composition. It is calculated as follows:

Permeability Stability Index=(GBP of processed sample)/(GBP of originalsample).

EXAMPLES

The following SAP Preproducts A, B, Aland G-J, Neutralized AluminumSalts C-F, Comparative Examples 1-5, and Examples 1-18 are provided toillustrate the inventions of products including particulatesuperabsorbent polymer composition and processes to make particulatesuperabsorbent polymer composition as set forth in the claims, and donot limit the scope of the claims. Unless otherwise stated all parts,and percentages are based on the dry particulate superabsorbent polymercomposition.

SAP Preproduct A

A superabsorbent polymer may be made in the following way. Into apolyethylene vessel equipped with an agitator and cooling coils wasadded, 2.0 kg of 50% NaOH and 3.32 kg of distilled water and cooled to20° C. 0.8 kg of glacial acrylic acid was then added to the causticsolution and the solution again cooled to 20° C. 4.8 g of polyethyleneglycol monoallylether acrylate, 4.8 g of ethoxylated trimethylol propanetriacrylate SARTOMER® 454 product, and 1.6 kg of glacial acrylic acidwere added to the first solution, followed by cooling to 4-6° C.Nitrogen was bubbled through the monomer solution for about 5 minutes.The monomer solution was then discharged into a rectangular tray. 80 gof 1% by weight of H₂O₂ aqueous solution, 120 g of 2 wt % aqueous sodiumpersulfate solution, and 72 g of 0.5 wt % aqueous sodium erythorbatesolution was added into the monomer solution to initiate polymerizationreaction. The agitator was stopped and the initiated monomer was allowedto polymerize for 20 minutes.

A particulate superabsorbent polymer may be prepared as follows. Theresulting hydrogel was chopped and extruded with a Hobart 4M6 commercialextruder, followed by drying in a Procter & Schwartz Model 062 forcedair oven at 175° C. for 12 minutes with up flow and 6 minutes with downflow air on a 20 inch×40 inch perforated metal tray to a final productmoisture level of less than 5 wt %. The dried material was coarse-groundin a Prodeva Model 315-S crusher, milled in an MPI 666-F three-stageroller mill and sieved with a Minox MTS 600DS3V to remove particlesgreater than 850 μm and smaller than 150 μm. The obtained Preproduct Acontained 4.0% of moisture.

SAP Preproduct B

A superabsorbent polymer may be made in the following way. Into apolyethylene vessel equipped with an agitator and cooling coils wasadded, 1.9 kg of 50% NaOH and 3.34 kg of distilled water and cooled to20° C. 0.83 kg of glacial acrylic acid was then added to the causticsolution and the solution again cooled to 20° C. 4.46 g of polyethyleneglycol monoallylether acrylate, 4.46 g of ethoxylated trimethylolpropane triacrylate SARTOMER® 454 product, and 1.65 kg of glacialacrylic acid were added to the first solution, followed by cooling to4-6° C. Nitrogen was bubbled through the monomer solution for about 5minutes. The monomer solution was then discharged into a rectangulartray. 80 g of 1% by weight of H₂O₂ aqueous solution, 120 g of 2 wt %aqueous sodium persulfate solution, and 72 g of 0.5 wt % aqueous sodiumerythorbate solution was added into the monomer solution to initiatepolymerization reaction. The agitator was stopped and the initiatedmonomer was allowed to polymerize for 20 minutes.

A particulate superabsorbent polymer may be prepared as follows. Theresulting hydrogel was chopped and extruded with a Hobart 4M6 commercialextruder, followed by drying in a Procter & Schwartz Model 062 forcedair oven at 175° C. for 12 minutes with up flow and 6 minutes with downflow air on a 20 inch×40 inch perforated metal tray to a final productmoisture level of less than 5 wt %. The dried material was coarse-groundin a Prodeva Model 315-S crusher, milled in an MPI 666-F three-stageroller mill and sieved with a Minox MTS 600DS3V to remove particlesgreater than 850 μm and smaller than 150 μm. The obtained Preproduct Bcontained 4.3% of moisture.

SAP Preproduct A1

A superabsorbent polymer may be made in the following way. Into apolyethylene vessel equipped with an agitator and cooling coils wasadded, 2.0 kg of 50% NaOH and 3.32 kg of distilled water and cooled to20° C. 0.8 kg of glacial acrylic acid was then added to the causticsolution and the solution again cooled to 20° C. 4.8 g of polyethyleneglycol monoallylether acrylate, 4.8 g of ethoxylated trimethylol propanetriacrylate SARTOMER® 454 product, and 1.6 kg of glacial acrylic acidwere added to the first solution, followed by cooling to 4-6° C.Nitrogen was bubbled through the monomer solution for about 5 minutes.The monomer solution was then discharged into a rectangular tray. 80 gof 1% by weight of H20 2 aqueous solution, 120 g of 2 wt % aqueoussodium persulfate solution, and 72 g of 0.5 wt % aqueous sodiumerythorbate solution was added into the monomer solution to initiatepolymerization reaction. The agitator was stopped and the initiatedmonomer was allowed to polymerize for 20 minutes.

A particulate superabsorbent polymer may be prepared as follows. Theresulting hydrogel was chopped and extruded with a Hobart 4M6 commercialextruder, followed by drying in a Procter & Schwartz Model 062 forcedair oven at 175° C. for 12 minutes with up flow and 6 minutes with downflow air on a 20 inch×40 inch perforated metal tray to a final productmoisture level of less than 5 wt %. The dried material was coarse-groundin a Prodeva Model 315-S crusher, milled in an MPI 666-F three-stageroller mill and sieved with a Minox MTS 600DS3V to remove particlesgreater than 700 μm and smaller than 150 μm. The obtained Preproduct A1contained 12% of particles larger than 600 μm. The moisture content ofthe obtained Preproduct A1 was measured as 4.0%.

SAP Preproduct G

A superabsorbent polymer may be made in the following way. Into apolyethylene vessel equipped with an agitator and cooling coils wasadded, 1.93 kg of 50% NaOH and 2.71 kg of deionized water and cooled to20° C. 0.83 kg of glacial acrylic acid was then added to the causticsolution and the solution again cooled to 20° C. 4.96 g of polyethyleneglycol monoallylether acrylate, 4.96 g of ethoxylated trimethylolpropane triacrylate SARTOMER® 454 product, and 1.65 kg of glacialacrylic acid were added to the first solution, followed by cooling to4-6° C. Nitrogen was bubbled through the monomer solution for about 5minutes. A separate solution was prepared by dissolving 18.23 g sodiumbicarbonate, 0.151 gTween80, and 0.151 g Span20, in 0.58 kg of water.The mixture was added to the monomer solution and mixed with a SilversonHigh Shear Mixer at 7500 RPM for 40 seconds. The monomer solution wasthen discharged into a rectangular tray. 80 g of 1% by weight of H20 2aqueous solution, 120 g of 2 wt % aqueous sodium persulfate solution,and 72 g of 0.5 wt % aqueous sodium erythorbate solution was added intothe monomer solution to initiate polymerization reaction. The agitatorwas stopped and the initiated monomer was allowed to polymerize for 20minutes.

The resulting hydrogel was chopped and extruded with a Hobart 4M6commercial extruder, followed by drying in a Procter & Schwartz Model062 forced air oven at 175° C. for 13 minutes with up flow and 7 minuteswith down flow air on a 20 inch×40 inch perforated metal tray to a finalproduct moisture level of less than 5 wt %. The dried material wascoarse-ground in a Prodeva Model 315-S crusher, milled in an MPI 666-Fthree-stage roller mill and sieved with a Minox MTS 600DS3V to removeparticles greater than 700 μm and smaller than 150 μm. The obtainedPreproduct G contained between 10 and 14% of particles larger than 600μm.

SAP Preproduct H

A superabsorbent polymer may be made in the following way. Into apolyethylene vessel equipped with an agitator and cooling coils wasadded, 2.01 kg of 50% NaOH and 3.21 kg of distilled water and cooled to20° C. 0.83 kg of glacial acrylic acid was then added to the causticsolution and the solution again cooled to 20° C. 14.88 g of polyethyleneglycol 300 diacrylate, 4.96 g of Dynasylan 6490, and 1.65 kg of glacialacrylic acid were added to the first solution, followed by cooling to4-6° C. Nitrogen was bubbled through the monomer solution for about 5minutes. The monomer solution was then discharged into a rectangulartray. 80 g of 1% by weight of H20 2 aqueous solution, 120 g of 2 wt %aqueous sodium persulfate solution, and 72 g of 0.5 wt % aqueous sodiumerythorbate solution was added into the monomer solution to initiatepolymerization reaction. The agitator was stopped and the initiatedmonomer was allowed to polymerize for 20 minutes.

A particulate superabsorbent polymer may be prepared as follows. Theresulting hydrogel was chopped and extruded with a Hobart 4M6 commercialextruder, followed by drying in a Procter & Schwartz Model 062 forcedair oven at 175° C. for 12 minutes with up flow and 6 minutes with downflow air on a 20 inch×40 inch perforated metal tray to a final productmoisture level of less than 5 wt %. The dried material was coarse-groundin a Prodeva Model 315-S crusher, milled in an MPI 666-F three-stageroller mill and sieved with a Minox MTS 600DS3V to remove particlesgreater than 700 μm and smaller than 150 μm. The obtained Preproduct Hcontained 10 and 14% of particles larger than 600 μm.

SAP Preproduct I

A superabsorbent polymer may be made in the following way. Into apolyethylene vessel equipped with an agitator and cooling coils wasadded, 1.93 kg of 50% NaOH and 3.31 kg of distilled water and cooled to20° C. 0.83 kg of glacial acrylic acid was then added to the causticsolution and the solution again cooled to 20° C. 3.97 g of polyethyleneglycol 300 diacrylate, 6.45 g of Dynasylan 6490, and 1.65 kg of glacialacrylic acid were added to the first solution, followed by cooling to4-6° C. Nitrogen was bubbled through the monomer solution for about 5minutes. The monomer solution was then discharged into a rectangulartray. 80 g of 1% by weight of H20 2 aqueous solution, 120 g of 2 wt %aqueous sodium persulfate solution, and 72 g of 0.5 wt % aqueous sodiumerythorbate solution was added into the monomer solution to initiatepolymerization reaction. The agitator was stopped and the initiatedmonomer was allowed to polymerize for 20 minutes.

A particulate superabsorbent polymer may be prepared as follows. Theresulting hydrogel was chopped and extruded with a Hobart 4M6 commercialextruder, followed by drying in a Procter & Schwartz Model 062 forcedair oven at 175° C. for 12 minutes with up flow and 6 minutes with downflow air on a 20 inch×40 inch perforated metal tray to a final productmoisture level of less than 5 wt %. The dried material was coarse-groundin a Prodeva Model 315-S crusher, milled in an MPI 666-F three-stageroller mill and sieved with a Minox MTS 600DS3V to remove particlesgreater than 700 μm and smaller than 150 μm. The obtained Preproduct Icontained 10 and 14% of particles larger than 600 μm.

SAP Preproduct J

A superabsorbent polymer may be made in the following way. Into apolyethylene vessel equipped with an agitator and cooling coils wasadded, 1.93 kg of 50% NaOH and 2.70 kg of distilled water and cooled to20° C. 0.83 kg of glacial acrylic acid was then added to the causticsolution and the solution again cooled to 20° C. 7.69 g of polyethyleneglycol 300 diacrylate, 8.18 g of Dynasylan 6490, and 1.65 kg of glacialacrylic acid were added to the first solution, followed by cooling to4-6° C. Nitrogen was bubbled through the monomer solution for about 5minutes. A separate solution was prepared by dissolving 18.27 g sodiumbicarbonate, 0.151 g Tween80, and 0.151 g Span20, in 0.58 kg of water.The mixture was added to the monomer solution and mixed with a SilversonHigh Shear Mixer at 7500 RPM for 40 seconds. The monomer solution wasthen discharged into a rectangular tray. 80 g of 1% by weight of H₂O₂aqueous solution, 120 g of 2 wt % aqueous sodium persulfate solution,and 72 g of 0.5 wt % aqueous sodium erythorbate solution was added intothe monomer solution to initiate polymerization reaction. The agitatorwas stopped and the initiated monomer was allowed to polymerize for 20minutes.

A particulate superabsorbent polymer may be prepared as follows. Theresulting hydrogel was chopped and extruded with a Hobart 4M6 commercialextruder, followed by drying in a Procter & Schwartz Model 062 forcedair oven at 175° C. for 12 minutes with up flow and 6 minutes with downflow air on a 20 inch×40 inch perforated metal tray to a final productmoisture level of less than 5 wt %. The dried material was coarse-groundin a Prodeva Model 315-S crusher, milled in an MPI 666-F three-stageroller mill and sieved with a Minox MTS 600DS3V to remove particlesgreater than 700 μm and smaller than 150 μm. The obtained Preproduct Jcontained 10 and 14% of particles larger than 600 μm.

Neutralized Aluminum Salt C

200 g of aluminum sulfate solution (20% aqueous solution) was stirred ina beaker with a magnetic stirring bar. To this solution was added sodiumhydroxide solution (50% aqueous solution) until the pH of the mixturereached 7. Totally 130 g of sodium hydroxide solution was consumed. Thewhite colloidal suspension was stirred for 15 minutes and furthersheared with Tumax mixer for about 1 minute to break down clumps. Theneutralized aluminum solution was used for SAP modification withoutfurther purification.

Neutralized Aluminum Salt D

120 g of aluminum sulfate solution (20% aqueous solution) was stirred ina beaker with a magnetic stirring bar. To this solution was added sodiumaluminate solution (20% aqueous solution) until the pH of the mixturereached 6.5. Totally 60 g of sodium aluminate solution was consumed. Thewhite colloidal suspension was stirred for 15 minutes and furthersheared with Tumax mixer for about 1 minute to break down clumps. Theneutralized aluminum solution was used for SAP modification withoutfurther purification.

Neutralized Aluminum Salt E

To a 1000-ml beaker were added 49 g of lactic acid (88%, commerciallyavailable from ADM) and 161.5 g of water. The beaker was cooled in anice bath and the solution was stirred with a magnetic stirring bar. Asolution of sodium aluminate (73.2 g, 43% wt/wt in water) was added intothe beaker. Then a solution of aluminum sulfate hydrate (59.3 g, 48%wt/wt in water) was added into the beaker. The resulting mixture was aclear solution with a pH value of 6.3. The neutralized aluminum saltsolution obtained was used for SAP surface modification.

Neutralized Aluminum Salt F

To a 1000-ml beaker were added 19.2 g of glycolic acid (commerciallyavailable from Sigma-Aldrich) and 130.1 g of water. The beaker wascooled in an ice bath and the solution was stirred with a magneticstirring bar. A solution of sodium aluminate (103.7 g, 20% wt/wt inwater) was added into the beaker. Then a solution of aluminum sulfatehydrate (44.9 g, 40% wt/wt in water) was added into the beaker. Theresulting mixture was a clear solution with a pH value of 6.0. Theneutralized aluminum salt solution obtained was used for SAP surfacemodification.

Comparative Example 1

4 g of aluminum sulfate hydrate solution (48% wt/wt in water) and 12 gof ethylene carbonate solution (33% wt/wt in water) were applied on thesurface of 400 g of SAP Preproduct A using a finely atomized spray froma Paasche VL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as0.1%. The average AAP(0.7 psi) of the product is 21.7.

Comparative Example 2

6 g of sodium aluminate solution (33% wt/wt in water) and 12 g ofethylene carbonate solution (33% wt/wt in water) were applied on thesurface of 400 g of SAP Preproduct A using a finely atomized spray froma Paasche VL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as0.2%. The average AAP(0.7 psi) of the product is 20.7.

Comparative Example 3

16 g of neutralized aluminum salt solution C and 8 g of ethylenecarbonate solution (50% wt/wt in water) were applied on the surface of400 g of SAP Preproduct A using a finely atomized spray from a PaascheVL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as0.13%. The average AAP(0.7 psi) of the product is 20.1.

Comparative Example 4

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct A using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 55 minutes for surfacecrosslinking. The surface crosslinked particulate material was thensieved with 20/100 mesh US standard sieves to remove particles greaterthan 850 μm and smaller than 150 μm. The moisture content of the productobtained was measured as 0.2%. The average AAP(0.7 psi) of the productis 19.7.

Comparative Example 5

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct A using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 55 minutes for surfacecrosslinking. The surface crosslinked particulate material was cooleddown to below 60° C. 11.4 g of neutralized aluminum salt solution E, 0.4g of polyethylene glycol (molecular weight 8000), and 8.0 g of deionizedwater were mixed to give a clear solution. The resulting mixture wasapplied on the surface crosslinked particulate material using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was relaxedat room temperature for one day and then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as2.3%. The average AAP(0.7 psi) of the product is 21.7.

Example 1

16 g of neutralized aluminum salt solution C and 8 g of ethylenecarbonate solution (50% wt/wt in water) were applied on the surface of400 g of SAP Preproduct A using a finely atomized spray from a PaascheVL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as0.13%. The surface crosslinked particulate material was cooled down tobelow 60° C. and coated with a solution containing 0.4 g of polyethyleneglycol (molecular weight 8000) and 40 g of deionized water. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The moisture content of the product obtainedwas measured as 7.9%. The average AAP(0.7 psi) of the product is 18.8.

Example 2

16 g of neutralized aluminum salt solution C and 8 g of ethylenecarbonate solution (50% wt/wt in water) were applied on the surface of400 g of SAP Preproduct A using a finely atomized spray from a PaascheVL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as0.13%. The surface crosslinked particulate material was cooled down tobelow 60° C. and coated with a solution containing 0.4 g of polyethyleneglycol (molecular weight 8000), 1.6 g of sodium lactate and 40 g ofdeionized water. The coated material was relaxed at room temperature forone day and then sieved with 20/100 mesh US standard sieves to removeparticles greater than 850 μm and smaller than 150 μm. The moisturecontent of the product obtained was measured as 7.9%. The averageAAP(0.7 psi) of the product is 18.9.

Example 3

16 g of neutralized aluminum salt solution C and 8 g of ethylenecarbonate solution (50% wt/wt in water) were applied on the surface of400 g of SAP Preproduct A using a finely atomized spray from a PaascheVL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as0.13%. The surface crosslinked particulate material was cooled down tobelow 60° C. and coated with a solution containing 0.4 g of polyethyleneglycol (molecular weight 8000), 1.6 g of sodium gluconate and 40 g ofdeionized water. The coated material was relaxed at room temperature forone day and then sieved with 20/100 mesh US standard sieves to removeparticles greater than 850 μm and smaller than 150 μm. The moisturecontent of the product obtained was measured as 7.8%. The averageAAP(0.7 psi) of the product is 18.9.

Example 4

16 g of neutralized aluminum salt solution D and 8 g of ethylenecarbonate solution (50% wt/wt in water) were applied on the surface of400 g of SAP Preproduct A using a finely atomized spray from a PaascheVL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as0.13%. The surface crosslinked particulate material was cooled down tobelow 60° C. and coated with a solution containing 0.4 g of polyethyleneglycol (molecular weight 8000) and 40 g of deionized water. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The moisture content of the product obtainedwas measured as 7.5%. The average AAP(0.7 psi) of the product is 18.7.

Example 5

16 g of neutralized aluminum salt solution D and 8 g of ethylenecarbonate solution (50% wt/wt in water) were applied on the surface of400 g of SAP Preproduct A using a finely atomized spray from a PaascheVL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as0.13%. The surface crosslinked particulate material was cooled down tobelow 60° C. and coated with a solution containing 0.4 g of polyethyleneglycol (molecular weight 8000), 1.6 g of sodium lactate and 40 g ofdeionized water. The coated material was relaxed at room temperature forone day and then sieved with 20/100 mesh US standard sieves to removeparticles greater than 850 μm and smaller than 150 μm. The moisturecontent of the product obtained was measured as 7.6%. The averageAAP(0.7 psi) of the product is 18.6.

Example 6

16 g of neutralized aluminum salt solution D and 8 g of ethylenecarbonate solution (50% wt/wt in water) were applied on the surface of400 g of SAP Preproduct A using a finely atomized spray from a PaascheVL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was then sieved with 20/100 mesh USstandard sieves to remove particles greater than 850 μm and smaller than150 μm. The moisture content of the product obtained was measured as0.13%. The surface crosslinked particulate material was cooled down tobelow 60° C. and coated with a solution containing 0.4 g of polyethyleneglycol (molecular weight 8000), 1.6 g of sodium gluconate and 40 g ofdeionized water. The coated material was relaxed at room temperature forone day and then sieved with 20/100 mesh US standard sieves to removeparticles greater than 850 μm and smaller than 150 μm. The moisturecontent of the product obtained was measured as 7.8%. The averageAAP(0.7 psi) of the product is 18.2.

Example 7

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct A using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 55 minutes for surfacecrosslinking. The surface crosslinked particulate material was cooleddown to below 60° C. 11.4 g of neutralized aluminum salt solution E, 0.4g of polyethylene glycol (molecular weight 8000), and 28.0 g ofdeionized water were mixed to give a clear solution. The resultingmixture was applied on the surface crosslinked particulate materialusing a finely atomized spray from a Paasche VL sprayer while the SAPparticles were fluidized in air and continuously mixed. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The product obtained contained 33% ofparticles larger than 600 μm. The moisture content of the product wasmeasured as 7 0.1%. The average AAP(0.7 psi) of the product is 19.7.

Example 8

Same as Example 9 except the sieves were changed to 25/100 mesh USstandard sieves. The product obtained contained 12% of particles largerthan 600 μm. The moisture content of the product was measured as 7.5%.The average AAP(0.7 psi) of the product is 19.0.

Example 9

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct B using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 30 minutes for surfacecrosslinking. The surface crosslinked particulate material was cooleddown to below 60° C. 11.4 g of neutralized aluminum salt solution E, 0.4g of polyethylene glycol (molecular weight 8000), and 28.0 g ofdeionized water were mixed to give a clear solution. The resultingmixture was applied on the surface crosslinked particulate materialusing a finely atomized spray from a Paasche VL sprayer while the SAPparticles were fluidized in air and continuously mixed. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The product obtained contained 25% ofparticles larger than 600 μm. The moisture content of the product wasmeasured as 7.7%. The average AAP(0.7 psi) of the product is 20.3.

Example 10

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct A using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 55 minutes for surfacecrosslinking. The surface crosslinked particulate material was cooleddown to below 60° C. 11.4 g of neutralized aluminum salt solution E, 0.4g of polyethylene glycol (molecular weight 8000), and 40.0 g ofdeionized water were mixed to give a clear solution. The resultingmixture was applied on the surface crosslinked particulate materialusing a finely atomized spray from a Paasche VL sprayer while the SAPparticles were fluidized in air and continuously mixed. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The moisture content of the product wasmeasured as 11%. The average AAP(0.7 psi) of the product is 19.6.

Example 11

4 g of ethylene carbonate was dissolved in 19.7 g of neutralizedaluminum salt solution F and the mixture was applied on the surface of400 g of SAP Preproduct A using a finely atomized spray from a PaascheVL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was then heated in a convectionoven at 185° C. for 55 minutes for surface crosslinking. The surfacecrosslinked particulate material was cooled down to below 60° C. 12 g ofneutralized aluminum salt solution F, 0.4 g of polyethylene glycol(molecular weight 8000), and 32.0 g of deionized water were mixed togive a clear solution. The resulting mixture was applied on the surfacecrosslinked particulate material using a finely atomized spray from aPaasche VL sprayer while the SAP particles were fluidized in air andcontinuously mixed. The coated material was relaxed at room temperaturefor one day and then sieved with 20/100 mesh US standard sieves toremove particles greater than 850 μm and smaller than 150 μm. Themoisture content of the product was measured as 8.5%. The averageAAP(0.7 psi) of the product is 19.0.

Example 12

16 g of ethylene carbonate solution (25% wt/wt in water) was applied onthe surface of 400 g of SAP Preproduct A using a finely atomized sprayfrom a Paasche VL sprayer while the SAP particles were fluidized in airand continuously mixed. The coated material was then heated in aconvection oven at 185° C. for 55 minutes for surface crosslinking. Thesurface crosslinked particulate material was cooled down to below 60° C.11.4 g of neutralized aluminum salt solution E, 0.4 g of polyethyleneglycol (molecular weight 8000), and 24.0 g of deionized water were mixedto give a clear solution. The resulting mixture was applied on thesurface crosslinked particulate material using a finely atomized sprayfrom a Paasche VL sprayer while the SAP particles were fluidized in airand continuously mixed. The coated material was relaxed at roomtemperature for one day and then sieved with 20/100 mesh US standardsieves to remove particles greater than 850 μm and smaller than 150 μm.The product obtained contained 25% of particles larger than 600 μm. Themoisture content of the product was measured as 7.7%. The averageAAP(0.7 psi) of the product is 18.5.

Example 13

Same as Example 12 except that neutralized aluminum salt solution F wasused instead of E. The moisture content of the product obtained wasmeasured as 6%. The average AAP(0.7 psi) of the product is 19.3.

Example 14

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct A1 using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 45 minutes for surfacecrosslinking. The surface crosslinked particulate material was cooleddown to below 60° C. 11.4 g of neutralized aluminum salt solution E, 0.4g of polyethylene glycol (molecular weight 8000), and 28.0 g ofdeionized water were mixed to give a clear solution. The resultingmixture was applied on the surface crosslinked particulate materialusing a finely atomized spray from a Paasche VL sprayer while the SAPparticles were fluidized in air and continuously mixed. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The product obtained contained 7.9% ofparticles larger than 600 μm and had a mean PSD of 398 μm. The moisturecontent of the product was measured as 7.0%. Properties of the productincluded a CRC of 30.2 g/g, AUL(0.9 psi) of 17.8 g/g, AAP(0.7 psi) of18.9 g/g, and a GBP of 46.2×10⁻⁸ cm².

Example 15

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct G using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 55 minutes for surfacecrosslinking. The surface crosslinked particulate material was cooleddown to below 60° C. 11.4 g of neutralized aluminum salt solution E, 0.4g of polyethylene glycol (molecular weight 8000), and 32.0 g ofdeionized water were mixed to give a clear solution. The resultingmixture was applied on the surface crosslinked particulate materialusing a finely atomized spray from a Paasche VL sprayer while the SAPparticles were fluidized in air and continuously mixed. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The product obtained contained 5.5% ofparticles larger than 600 μm and had a mean PSD of 397 μm. The moisturecontent of the product was measured as 7.3%. The average AAP(0.7 psi) ofthe product is 18.2 g/g, and the Vortex time of Example 15 is 27seconds.

Example 16

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct H using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 55 minutes for surfacecrosslinking. The surface crosslinked particulate material was cooleddown to below 60° C. 11.4 g of neutralized aluminum salt solution E, 0.4g of polyethylene glycol (molecular weight 8000), and 32.0 g ofdeionized water were mixed to give a clear solution. The resultingmixture was applied on the surface crosslinked particulate materialusing a finely atomized spray from a Paasche VL sprayer while the SAPparticles were fluidized in air and continuously mixed. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The product obtained contained 7.4% ofparticles larger than 600 μm and had a mean PSD of 398 μm. The moisturecontent of the product was measured as 7.8%. The average AAP(0.7 psi) ofthe product is 21.3 g/g, and the Vortex time of Example 16 is 85 secondsand the CRCI is 4.1 g/g.

Example 17

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct I using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 55 minutes for surfacecrosslinking. The surface crosslinked particulate material was cooleddown to below 60° C. 11.4 g of neutralized aluminum salt solution E, 0.4g of polyethylene glycol (molecular weight 8000), and 32.0 g ofdeionized water were mixed to give a clear solution. The resultingmixture was applied on the surface crosslinked particulate materialusing a finely atomized spray from a Paasche VL sprayer while the SAPparticles were fluidized in air and continuously mixed. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The product obtained contained 9.0% ofparticles larger than 600 μm and had a mean PSD of 425 μm. The moisturecontent of the product was measured as 7.8%. The average AAP(0.7 psi) ofthe product is 19.1 g/g, and the Vortex time of Example 17 is 77 secondsand the CRCI is 8.6 g/g.

Example 18

11.4 g of neutralized aluminum salt solution E was mixed with 12 g ofethylene carbonate solution (33% wt/wt in water). The mixture wasapplied on the surface of 400 g of SAP Preproduct J using a finelyatomized spray from a Paasche VL sprayer while the SAP particles werefluidized in air and continuously mixed. The coated material was thenheated in a convection oven at 185° C. for 45 minutes for surfacecrosslinking. The surface crosslinked particulate material was cooleddown to below 60° C. 11.4 g of neutralized aluminum salt solution E, 0.4g of polyethylene glycol (molecular weight 8000), and 32.0 g ofdeionized water were mixed to give a clear solution. The resultingmixture was applied on the surface crosslinked particulate materialusing a finely atomized spray from a Paasche VL sprayer while the SAPparticles were fluidized in air and continuously mixed. The coatedmaterial was relaxed at room temperature for one day and then sievedwith 20/100 mesh US standard sieves to remove particles greater than 850μm and smaller than 150 μm. The product obtained contained 15.1% ofparticles larger than 600 μm and had a mean PSD of 441 μm. The moisturecontent of the product was measured as 8.9%. The average AAP(0.7 psi) ofthe product is 19.5 g/g, and the Vortex time of Example 18 is 35 secondsand the CRCI is 7.5 g/g.

TABLE 2 Particulate 0.9 AUL GBP after superabsorbent pH of 0.9 GBP CRCafter after processing Permeability polymer Al salt CRC AUL (×10⁻⁸processing processing (×10⁻⁸ stability Compressibility composition AlSalt solution (g/g) (g/g) cm²) (g/g) (g/g) cm²) index (mm²/N)Comparative Al₂(SO₄)₃ 2.8 32.2 20.2 14 35.5 13.9 3 0.19 n.d. Example 1Comparative NaAlO2 14 31.8 19.6 5 35.3 12.2 0.9 0.17 n.d. Example 2Comparative C 7 32.6 17.9 31 35.2 13.5 8 0.28 1.0 Example 3 ComparativeE 6.3 30.7 18.7 54 31 16 11 0.20 0.8 Example 4 Comparative E 6.3 29.8 1968 30.3 18.5 32 0.47 1.15 Example 5 Example 1 C 7 29.2 16.3 23 29.5 16.119 0.81 1.8 Example 2 C 7 28.7 16.7 26 29.3 16.2 18 0.70 1.7 Example 3 C7 28.6 17.2 24 29.6 16.2 19 0.78 1.4 Example 4 D 6.5 29.5 16 40 30.115.7 32 0.81 1.5 Example 5 D 6.5 28.8 16 42 29.8 15.4 30 0.73 1.7Example 6 D 6.5 28.6 16.2 41 30.0 14.9 29 0.71 3.2 Example 7 E 6.3 28.719.5 65 28.6 18.8 53 0.81 1.5 Example 8 E 6.3 28.8 19.4 68 29.1 19.2 580.85 1.3 Example 9 E 6.3 31.5 19 55 31.4 16.6 43 0.78 1.4 Example 10 E6.3 28.2 17.5 66 27.8 16.8 61 0.93 1.5 Example 11 F 6 28.8 17.3 53 30.216.1 50 0.95 1.8 Example 12 E 6.3 30.9 18.3 32 31.3 16.2 23 0.72 1.4Example 13 F 6 29.6 16.9 50 29.8 16.1 37 0.74 1.4 Example 14 E 6.3 30.217.8 46 29.9 16.7 31 0.67 1.3 Example 15 E 6.3 30 17.9 56.3 29.7 16.838.4 0.68 1.4

TABLE 3 CRC CRC CRC (rt, CRC Particulate (bt, (bt, 0.5 hr) (bt, 5 0.9AUL GBP after superabsorhent pH of 0.5 5 0.9 GBP after hr.) after afterprocessing Permeability polymer Al Al salt hr) hr) AUL (×10⁻⁸ processingprocessing processing (×10⁻⁸ stability Compressibility composition Saltsolution (g/g) (g/g) (g/g) cm²) (g/g) (g/g) (g/g) (cm²) index (mm²/N)Example 16 E 6.3 30.1 35.2 17.3 32.4 31 35.4 16.1 20.3 0.63 1.7 Example17 E 6.3 27.5 36.6 18.1 47.3 28 37.9 17.4 37.3 0.79 1.5 Example 18 E 6.328.8 36.1 19 58.4 28.6 35.9 18.3 42.6 0.73 1.3

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Other than in the operating examples, or where otherwiseindicated, all numbers expressing quantities of ingredients, reactionconditions, and so forth used in the specification and claims are to beunderstood as being modified in all instances by the term “about.” Anynumerical value, however, inherently contain certain errors necessarilyresulting from the standard deviation found in their respective testingmeasurements.

1. A particulate superabsorbent polymer composition comprising aparticulate superabsorbent polymer comprising from about 0.05 to about2.0 wt. % based on the total amount of the polymerizable unsaturatedacid group containing monomer solution of a foaming agent, and fromabout 0.001 to about 1.0 wt. % based on the total amount of thepolymerizable unsaturated acid group containing monomer solution of amixture of a lipophile surfactant and a polyethoxylated hydrophilicsurfactant, and from 0.01 wt % to about 5 wt % based on the particulatesuperabsorbent polymer composition weight of a neutralized aluminum saltapplied to the surface of the particulate superabsorbent polymer, in theform of an aqueous neutralized aluminum salt solution having a pH valuefrom about 5.5 to about 8; wherein the particulate superabsorbentpolymer composition has a Centrifuge Retention Capacity (CRC) of fromabout 25 grams to about 40 grams of 0.9 weight percent sodium chlorideaqueous per gram of the particulate superabsorbent polymer composition,wherein the CRC is measured either before or after subjecting thesuperabsorbent polymer composition to a Processing Test, and anabsorbency under load at 0.9 psi prior to subjecting the particulatesuperabsorbent polymer composition to the Processing Test of from 15 g/gto 21 g/g; and a Free Swell Gel Bed Permeability (FSGBP) of from about30×10⁻⁸ cm² to about 200×10⁻⁸ cm² prior to subjecting the particulatesuperabsorbent polymer composition to the Processing Test; wherein theparticulate superabsorbent polymer composition has a Vortex time of from25 to 60 seconds as measured by the Vortex Test, and has a permeabilitystability index of from about 0.60 to about 0.99 when subjecting theparticulate superabsorbent polymer composition to a Processing Test anda compressibility of from 1.30 mm²/N to about 4 mm²/N as measured by theCompression Test.
 2. The particulate superabsorbent polymer compositionof claim 1 wherein the lipophile nonionic surfactant has a HLB of from 4to 9 and the polyethoxylated hydrophilic nonionic surfactant has a HLBof from 12 to
 18. 3. The particulate superabsorbent polymer compositionof claim 1 wherein the mixture of a lipophile nonionic surfactant and apolyethoxylated hydrophilic nonionic surfactant has a HLB of from 8 to14.
 4. The particulate superabsorbent polymer of claim 3 wherein thelipophile nonionic surfactant is a sorbitan ester and thepolyethoxylated hydrophilic nonionic surfactant is a polyethoxylatedsorbitan ester.
 5. The particulate superabsorbent polymer composition ofclaim 1 comprising an internal crosslinker agent comprising a silanecompound comprising at least one vinyl group or allyl group and at leastone Si—0 bond wherein the vinyl group or allyl group is directlyattached to a silicon atom, wherein the particulate superabsorbentpolymer composition has a Centrifuge Retention Capacity (CRC) Increaseof at least 2 g/g based onCRC Increase=CRC(bt,5 hr)−CRC(rt,0.5 hr) wherein CRC Increase measuresthe increase in the CRC that occurs and is calculated as the differencebetween the second CRC Test and first CRC Test, and bt refers to bodytemperature and rt refers to room temperature.
 6. The particulatesuperabsorbent polymer composition of claim 5 wherein said silanecompound is selected from one of the following

wherein R₁ represents C₂ to C₃ alkenyl, R₂ represents H, C₁ to C₄ alkyl,C₂ to C₅ alkenyl, C₆ to C₈ aryl, C₂ to C₅ carbonyl, R₃ represents H, C₁to C₄ alkyl, C₆ to C₈ aryl, R₄ and R₅ independently represent H, C₁ toC₄ alkyl, C₆ to C₈ aryl, m represents an integer of from 1 to 2, nrepresents an integer of from 2 to 3, l represents an integer of from 0to 1, m+n+1=4, x represents an integer larger than 1, and y representsan integer of 0 or larger than
 0. 7. The particulate superabsorbentpolymer composition of claim 6 wherein said silane compound is selectedfrom vinyltriisopropenoxy silane, vinyltriacetoxysilane,vinyltrimethoxysilane, vinyltriethoxysilane, diethoxymethylvinyl silane,and polysiloxane comprising at least two vinyl groups.
 8. A particulatesuperabsorbent polymer composition comprising a particulatesuperabsorbent polymer comprising an internal crosslinker agentcomprising a silane compound comprising at least one vinyl group orallyl group and at least one Si—O bond wherein the vinyl group or allylgroup is directly attached to a silicon atom, and from 0.01 wt % toabout 5 wt % based on the particulate superabsorbent polymer compositionweight of a neutralized aluminum salt applied to the surface of theparticulate superabsorbent polymer, in the form of an aqueousneutralized aluminum salt solution having a pH value from about 5.5 toabout 8; wherein the particulate superabsorbent polymer composition hasa Centrifuge Retention Capacity (CRC) of from about 25 grams to about 40grams of 0.9 weight percent sodium chloride aqueous per gram of theparticulate superabsorbent polymer composition, wherein the CRC ismeasured either before or after subjecting the superabsorbent polymercomposition to a Processing Test, and an absorbency under load at 0.9psi prior to subjecting the particulate superabsorbent polymercomposition to the Processing Test of from 15 g/g to 21 g/g; and anoriginal Free Swell Gel Bed Permeability (FSGBP) of from about 30×10⁻⁸cm² to about 200×10⁻⁸ cm² prior to subjecting the particulatesuperabsorbent polymer composition to the Processing Test; and apermeability stability index of from about 0.60 to about 0.99 whensubjecting the particulate superabsorbent polymer composition to aProcessing Test, and a compressibility of from 1.30 mm²/N to about 4mm²/N as measured by the Compression Test, and a Centrifuge RetentionCapacity (CRC) Increase of at least 2 g/g or more based onCRC Increase=CRC(bt,5 hr)−CRC(rt,0.5 hr) wherein CRC Increase measuresthe increase in the CRC that occurs and is calculated as the differencebetween the second CRC Test and first CRC Test, and bt refers to bodytemperature and rt refers to room temperature.
 9. The particulatesuperabsorbent polymer composition of claim 8 wherein said silanecompound is selected from one of the following

wherein R₁ represents C₂ to C₃ alkenyl, R₂ represents H, C₁ to C₄ alkyl,C₂ to C₅ alkenyl, C₆ to C₈ aryl, C₂ to C₅ carbonyl, R₃ represents H, C₁to C₄ alkyl, C₆ to C₈ aryl, R₄ and R₅ independently represent H, C₁ toC₄ alkyl, C₆ to C₈ aryl, m represents an integer of from 1 to 2, nrepresents an integer of from 2 to 3, l represents an integer of from 0to 1, m+n+1=4, x represents an integer larger than 1, and y representsan integer of 0 or larger than
 0. 10. The particulate superabsorbentpolymer composition of claim 9 wherein said silane compound is selectedfrom vinyltriisopropenoxy silane, vinyltriacetoxysilane,vinyltrimethoxysilane, vinyltriethoxysilane, diethoxymethylvinyl silane,and polysiloxane comprising at least two vinyl groups.
 11. A process forthe production of a particulate superabsorbent polymer compositioncomprising the following steps: a) preparing an aqueous monomer solutionof a mixture of a polymerizable unsaturated acid group containingmonomer and an internal crosslinking agent monomer wherein the aqueousmonomer solution comprises dissolved oxygen; b) sparging the aqueousmonomer solution of step a) including adding an inert gas to the aqueousmonomer solution of step a) to replace the dissolved oxygen of theaqueous monomer solution; c) polymerizing the aqueous monomer solutionof step b) including the steps of c1) adding to the aqueous monomersolution of step a): i) an aqueous solution comprising from about 0.05to about 2.0 wt. % based on the total amount of the polymerizableunsaturated acid group containing monomer solution of a foaming agent;and ii) an aqueous solution comprising from about 0.001 to about 1.0 wt.% based on the total amount of the polymerizable unsaturated acid groupcontaining monomer solution of a mixture of a lipophile surfactant and apolyethoxylated hydrophilic surfactant; c2) treating the monomersolution of step c1) to high speed shear mixing to form a treatedmonomer solution, wherein the components i) an aqueous solutioncomprising from about 0.1 to about 1.0 wt. % of a foaming agent; and ii)an aqueous solution comprising from about 0.001 to about 1.0 wt. % of amixture of a lipophile surfactant and a polyethoxylated hydrophilicsurfactant are added to the aqueous monomer solution after step b) ofsparging the aqueous monomer solution and before step c2) of high speedshear mixing of the aqueous monomer solution; c3) forming a hydrogel byadding a polymerization initiator to the treated monomer solution ofstep c2) wherein the initiator is added to the treated monomer solutionafter the foaming agent and the mixture of surfactants, wherein thepolymer is formed to include bubbles of the foaming agent into thepolymer structure; and d) drying and grinding the hydrogel of step c) toform particulate superabsorbent polymer; and e) surface crosslinking theparticulate superabsorbent polymer of step d) with a surfacecrosslinking agent; b) preparing a neutralized aluminum salt in the formof an aqueous solution having a pH value from about 5.5 to about 8; and;c) applying the aqueous neutralized aluminum salt solution on thesurface of the particulate superabsorbent polymer composition; andwherein the particulate superabsorbent polymer composition has a degreeof neutralization of from about 50% mol to about 80 mol %; and theparticulate superabsorbent polymer composition has a CentrifugeRetention Capacity of from about 25 grams to about 40 grams of 0.9weight percent sodium chloride aqueous per gram of the particulatesuperabsorbent polymer composition, wherein the CRC is measured eitherbefore or after subjecting the particulate superabsorbent polymercomposition to a Processing Test, and an absorbency under load at 0.9psi prior to subjecting the particulate superabsorbent polymercomposition to the Processing Test of from 15 g/g to 21 g/g; and a FreeSwell Gel Bed Permeability (FSGBP) of about 30×10⁻⁸ cm² to about200×10⁻⁸ cm² prior to subjecting the treated particulate superabsorbentpolymer composition to the Processing Test; and wherein the particulatesuperabsorbent polymer composition has a permeability stability index offrom about 0.60 to about 0.99 when subjecting the particulatesuperabsorbent polymer composition to a Processing Test, and acompressibility from 0.30 mm²/N to about 4 mm²/N as measured by theCompression Test, and wherein the particulate superabsorbent polymercomposition has a vortex time of from about 25 sec to about 60 sec asmeasured by the Vortex Test.
 12. The process for making the particulatesuperabsorbent polymer composition according to claim 11 wherein saidaqueous aluminum salt solution has a pH value from about 6 to
 7. 13. Theprocess for making the particulate superabsorbent polymer compositionaccording to claim 11 wherein particles have a particle diameters ofsmaller than 600 μm and not smaller than 150 μm in an amount of not lessthan about 90 wt % of the particulate superabsorbent polymercomposition.
 14. The process for making the particulate superabsorbentpolymer composition according to claim 11 wherein said neutralizedaluminum salt is selected from: a) the reaction product of sodiumhydroxide with aluminum sulfate or aluminum sulfate hydrate; b) thereaction product of an organic acid with sodium aluminate; c) thereaction product of sodium aluminate with aluminum sulfate or aluminumsulfate hydrate; or d) the reaction product of an organic acid or itssalt with sodium aluminate and aluminum sulfate or aluminum sulfatehydrate.
 15. The process for making the particulate superabsorbentpolymer composition of claim 11 wherein the lipophile surfactant isnonionic and has a HLB of from 4 to 9 and the polyethoxylatedhydrophilic surfactant is nonionic and has a HLB of from 12 to
 18. 16.The process for making the particulate superabsorbent polymercomposition of claim 11 wherein the mixture of a lipophile surfactantand a polyethoxylated hydrophilic surfactant has a HLB of from 8 to 14.17. The process for making the particulate superabsorbent polymercomposition of claim 11 wherein the lipophile surfactant is a sorbitanester and the polyethoxylated hydrophilic surfactant is apolyethoxylated sorbitan ester.
 18. The process for making theparticulate superabsorbent polymer composition of claim 11 wherein thefoaming agent is selected from sodium carbonate or sodium bicarbonate.19. The process for making the particulate superabsorbent polymercomposition of claim 11 comprising from about 0.05 to about 1.0 wt. %based on the total amount of the polymerizable unsaturated acid groupcontaining monomer solution of the polymerization initiator.
 20. Theprocess for making the particulate superabsorbent polymer composition ofclaim 11 wherein the lipophile surfactant is nonionic and thepolyethoxylated hydrophilic surfactant is nonionic.
 21. The process formaking the particulate superabsorbent polymer of claim 11 wherein theinternal crosslinker agent comprises a silane compound comprising atleast one vinyl group or allyl group and at least one Si—O bond whereinthe vinyl group or allyl group is directly attached to a silicon atom,wherein the particulate superabsorbent polymer has a CentrifugeRetention Capacity (CRC) Increase of 2 g/g or more based onCRC Increase=CRC(bt,5 hr)−CRC(rt,0.5 hr) wherein CRC Increase measuresthe increase in the CRC that occurs and is calculated as the differencebetween the second CRC Test and first CRC Test, and bt refers to bodytemperature and rt refers to room temperature.
 22. The process formaking the particulate superabsorbent polymer composition of claim 21wherein said silane compound is selected from one of the following

wherein R₁ represents C₂ to C₃ alkenyl, R₂ represents H, C₁ to C₄ alkyl,C₂ to C₅ alkenyl, C₆ to C₈ aryl, C₂ to C₅ carbonyl, R₃ represents H, C₁to C₄ alkyl, C₆ to C₈ aryl, R₄ and R₅ independently represent H, C₁ toC₄ alkyl, C₆ to C₈ aryl, m represents an integer of from 1 to 2, nrepresents an integer of from 2 to 3, l represents an integer of from 0to 1, m+n+1=4, x represents an integer larger than 1, and y representsan integer of 0 or larger than
 0. 23. The process for making theparticulate superabsorbent polymer of claim 22 wherein said silanecompound is selected from vinyltriisopropenoxy silane,vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,diethoxymethylvinyl silane, and polysiloxane comprising at least twovinyl groups.